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J O U R N A L A. J. ALLMAND M.C. D.Sc. 0. L. BRADY D.Sc. A. W. CROSSLEY C.M.G. C.B.E. D. Sc. F. R. S. C. H. DESCH D. Sc. Y1i.D. M. 0. FORSTER D.Sc. Ph.D. F.R.S. I. M. HEILBRON D.S.O. D.Sc. Ph.D. J. 1'. HEWITT M.A. D.Sc. Ph.D. J. C. IRVINE C.B.E. D.Sc. F.R.S. H. KING D.Sc. F. R. 8. OF T. M. LOWRY C.B.E. D.Sc. F.R.S. J. W. MCBAIN M.A. Yh.D. J. I. 0. MASSON W.B.E. D.Sc. J. 0. PHILIP O.B.E. D.Sc. Ph.D. R. H. PICKARD B.Sc. Ph.D. F.R.S. N. V. SIDGW~CK M.A. Sc.D. F.R.S. J. F. THORPE C.B.E. D.Sc. F.R.S. Sir JAMES WAIXER D.Sc. LL.D. F. R. S. F.R.S. THE CHEMICAL SOCIETY. G. BARGER M.A. D.Sc. F.R.S. H. J. EVANS B.Sc. W. E. GARNER M.A. W. GODDEN B.Sc. C. R. HARINGTON B.A. C. K. INGOLD D.Sc. I<. KASHIMA I3g.S. J. KEENER D.Sc. Ph.D. W. 0. KERMACK M.A. B.Sc. H. KING D.Sc. S. I. LEVY B.A.B.Sc. S. S. MIHoLfC P1i.D. G. F. MORRELL D.Sc. P1i.D. J. R. PARTINGTOK M.B.E. D. Sc. T. H. POPE B.Sc. G. W. ROBINSON M.A. E. H. RODD D.Sc. F. M. EOWE D.Sc. W. P. SKERTCIILY. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER &LA. Sc.L). E. STEDMAN B.Sc. J. S. G. TIIoms D.Sc. W. THOMAS B.A. M.Sc. R. TRUS%RO~\.'SI~I B.Sc. D. F. TWISS D.Sc. J. C. WITHERS 1'h.D. H. WREN M.A. D.Sc. P1i.D. S. S. ZILVA D.Sc. Ph.D. 1922. Vol. CXXII. Part I. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1922.Abstractors of the Journal of the Society of Chewticat Industry who have contributed to this volume. J. I?. B~:IGCP. A. COUSEN. A. GROUNDS ALSc. A. J. HALL. C. IP~WIN. T. H. KURNHAM. J. K. FIRTH. J. H. LANE. H. MOORE. A. G. POLLARD. A. E. POWELL. J. REILLT. A. DE WAELE. €1. c. REYNARD. PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SOKS LIbIITED. BUNaAY SUPFOLK.

ISSN:0368-1769    

DOI:10.1039/CA92222FP001

出版商:RSC    

年代:1922

数据来源: RSC

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J O U R N A L A. J. ALLMAND M.C. D.Sc. 0. L. BRADY D.Sc. C. H. DESCH D.Sc. P1i.D. 31. 0. FORSTER D.8c. Ph.D. F.R.S. I. hf. HEILBRON D.S.O. D.Sc. Ph.D. J. T. HEWITT M.A. D.Sc. Ph.D. J. C. IRVINE C.B.E. D.So. F.R.S. 8. KING D.Sc. A. W. CROSSLEY C.M.G. C.B.E. D.Sc. F.R.S. F.R.S. OF T. M. LOWRY C.B.E. D.Sc. F.R.R. a. W. MCBAIN M.A. P1i.D. J. C. PHILIP O.B.E. D.Sc. Pli.D. B. H. PICKAN) D.Sc. Ph.D. F.R.R. N. V. SIDGJVICI; B.I.A. Sc.D. P. R. S. J. F. THOIWE C.B.E. D.Sc. P.R.S. Sir JAMES WALKET. D.Sc. LL.D. J. I. 0. MASSON M.B.E. D.SC. F.R.S. F. R. S. THE CHEMICAL S O C I E T Y 0. BARGEK M.A. D.Sc. F.R.S. H. J. EVANS B.Sc. W. E. GARNER M.A. w. GODDEN B.SC. C. R. HARINGTON B.A. C. K. INGOLD D.Sc. K. KASHIMA Rg.S. W. 0. KERMACK hL A B.Sc. H. KING D.Sc. 5. I. LEVY B.A. B.Sc. S. S. MIHOL~C Ph.D. G. F. hfORRELL D.Sc. Ph.D. J. R. PAETINGTON M.B. E. D.&. T. H. POPE B.Sc. J KENNER D.Sc. Ph.D. ABSTRACTS OF PAPERS G. W. ROBIXSON M.A. E. H. RODD D.Sc. F. &I. ROWE D.Sc. W. P. SKERTCHLY. J. F. SPENCER D.Sc. P1i.D. L. J. SPENCER M.A. Sc.D. E. STEDJIAS B.Sc. W. THOMAS B.A. KSc. R. TRUSZKOWSIII 13.S~. D. F. Tw~ss D.Sc. J. C. WITHERS P1i.D. H. WREN &LA. D.Sc. P1i.D. S. S. ZILTA D.Sc. Ph.D J. S. G . THOMAS D.Sc. LONDON GURNEY B JACKSON 33 PATERNOSTER ROW E.C.4. 1922.Abstractors of the Jourlznl of the Society of Chemical Zlzdustry who hare contributed t o this volume ,T. F. BKIGGS. 1’. Er. BUEXH-\JC. J. 13. FIRTH. A . Gaouxrw Ai.Sc. A. J. HALL. c. IRTVIF. i\. COUSEN. a. H. LANE. H. MOORE. A. G. POLLAED. A. R. POWELL. J. REILLY. H. C. REYNARD. A. DE WAELE.

ISSN:0368-1769    

DOI:10.1039/CA92222FP003

出版商:RSC    

年代:1922

数据来源: RSC

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ii. 44 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Molecular Volumes Physical Properties and Molecular Models of the Halogens. I?. A. HENGLEIN (2. anorg. Chem. 1921 118 165-171).-1t has been shown by Biltz (A. 1921 ii 437 487) that there is a linear relation between the molecular volumes of the halogens and of their compounds. It is now shown that there is likewise a linear relation between the atomic volumes of the halogens at their boiling points and others of their physical properties including melting point boiling point critical point latent heat of fusion or of evaporation and normal potential; also between the molecular volumes of the halogen acids a t the boiling point and many other of their physical constants. Owing to the close similarity in structure of the different halogen atoms their properties are determined principally by the atomic radius.In contrast with most groups of the periodic system the molecule of a halogen element has an especially simple structure; it can be represented diagrammatically by two cubes having a common edge with the valence electrons situated at the corners. E. H. R. The Catalytic Formation of Hydrogen Chloride from Hydrogen and Chlorine without Explosion. BERNHARD NEUMANN [with BERGDAHL BROY and KARWAT] (2. angew. Chem. 1921,34,613-620).-All non-explosion methods for the synthesis of hydrogen chloride gas yield a product contaminated with chlorine. Hoppe who first suggested the use of metallic chlorides as catalysts to this reaction employed the chlorides of aluminium tin and zinc in concentrated solution a t a temperature of 130".A repetition of his work has shown that under the most favourable conditions and with a very slow current of gas not more than 70% conversion is obtained. The reaction is favoured by an increase of concen- tration and of temperature but a practical limit is set to the latter by the point a t which evaporation becomes rapid. The author has used solid chlorides and higher temperatures. The hydrogen and chlorine were generated electrolytically in separate cells in the same electric circuit passing into a mixing flask containing water and thence to a quartz tube in the shape of a pipette filledINORGANIC CHEMISTRY. ii. 45 with granules of quartz impregnated with the selected chloride and heated. The emerging gases were absorbed in a 10-bulb potash tube.The mixed gases were shielded from light and drawn through the apparatus by uniform slight suction fluctuation of pressure being a source of explosions. With a low gas velocity a complete conversion was effected by magnesium chloride a t 300" by calcium chloride a t 305" by aluminium chloride (which a t this temperature is almost entirely decomposed) a t 350" and by quartz unimpregnated by any salt a t 380". Conversion was improved by warming the mixing flask to 50° with the effect of adding 1 mol. of water to each mol. of hydrogen chloride this temperature being an optimum. The dilution of the gases with oxygen had at 380" no influence on the reaction. The reactions Cl2+H,O=C1OH+HC1 ClOH+H,=H,O+HCl are considered to occur removal of the hydrogen chloride generated being facilitated Sulphate-free Sulphites for Standard Sulphur Dioxide Solutions.S. LANTZ SHENEFIELD PRANK C. VILBRANDT and JAMES R. WITHROW (Chem. and Net. Eng. 1921 25 953-955).- Pure sodium sulphite heptahydrate was prepared by passing care- fully purified sulphur dioxide into a solution of sodium carbonate to saturation adding the requisite amount of sodium carbonate to transform the resultant sodium hydrogen sulphite into the normal sulphite and cooling the solution to 0" whereby a crystalline meal of the heptahydrate was obtained. All the operations were carried out in the absence of oxygen and the damp crystals were found to be free from sulphate. They were placed in a desiccator over sulphuric acid and sodium pyrogallate was used as oxygen absorbent.Although every precaution was taken to exclude air leakage the crystals after one week contained 7.52% of sodium sulphate deca- hydrate. Similar oxidation occurred in the preparation of pure dry calcium sulphite and the opinion is expressed that in both cases this is due to autoxidation of the salt. It is concluded that the validity of all investigations in the literature based on the preparation of sulphate-free sulphite for use as a sulphur dioxide standard is doubtful. Polythionic Acids and Polythionates. E. H. RIESENFELD and G. W. FELD (2. anorg. Chem. 1921 119 225-270).-A method has been devised for estimating the proportions of tri- tetra- and penta-thionates together in solution with sulphite thiosulphate and sulphate and the method has been applied to the study of the formation and stability of the polythionates.The hexathionic acid described by Debus (T. 1888 53 278) does not exist. The total polythionic acids can be determined by treat- ment in neutral solution with a mercuric salt when four equivalents of sulphuric acid are produced for each molecule of polythionate for instance 2S,O,"+ 2Hg" + 4H,O =2HgS+ 4SO,"+ 8H'+4S. The acid can then be titrated. Alternatively the polythionates can be oxidised with bromine in alkaline solution; the whole of the sulphur is oxidised to sulphate and is precipitated and weighed by the partly dissociated chlorides. c. I. A. R. P.ii 46 ABSTRACTS OF CHEMICAL PAPERS. as barium sulphate. The trithionate is estimated by boiling the solution with an excess of copper sulphate when the following reaction occurs S306”+CU”+2H20=CUS+2~04”+4Ho The copper sulphide is filtered ignited and weighed as copper oxide.When boiled with excess of alkali the polythionates form thio- sulphate and sulphite thus 2S306”+60H’=~20,”+4~03’’+ 5X20,”+ 3H,O. The sulphite and thiosulphate formed are estim- ated by titration with iodine. By applying three of these reactions data can be obtained from which to calculate the proportions of tri- tetra- and penta-thionate present. The interaction between hydrogen sulphide and sulphur dioxide was studied by leading a current of the former as gas into an aqueous solution of the latter a t O” until a definite ratio of the reacting substances was present in solution. The total poly- thionate was estimated after sixty hours. The optimum ratio for polythionate formation was 2S0 1H2S.On the other hand with the ratio 2H2S SO all the sulphur was precipitated in the elementary form. Evidence was obtained that immediately after the prepar- ation of a solution in the ratio 2SO,:H,S an intermediate com- pound is formed which can be precipitated a t a low temperature as the barium salt; in solution this changes to barium thiosulphate. The proportion of tri- and tetra-thionic acids formed (determined after fourteen days) depends on the sulphur dioxide concentration the formation of tetrathionic acid being favoured by low concentration. The proportion of pentathionic acid is however practically con- stant. These results are contrary to those obtained by Heinze (A.1919 ii 334). The sulphuric acid which is always formed reaches a maximum near the commencement of the reaction; it must therefore he formed from the intermediate compound not by oxidation of the polythionic acids. Of the three polythionic acids the tetrathionic acid is the least stable and decomposes relatively quickly into tri- and penta- thionic acids. The trithionic acid decomposes more slowly with formation of sulphur dioxide whilst pentathionic acid decomposes only in the course of months with separation of sulphur. The order of stability is the same in neutral as in acid solution; in alkaline solution all the polythionates decompose quickly into thiosulphate and sulphite. The phenomena observed are explained on the assumption that the above intermediate compound is a hydrate of the unknown sulphur monoxide SO.This is stable in acid solution for a time but in neutral or alkaline solution quickly forms thiosulphate. In acid solution it slowly polymerises to pentathionic acid. By combination with sulphurous acid it forms tri- and tetra-thionic acid 3SO+H,S0,=.H,S,06 ; S0+2S02+H20=H2S306. By hydrogen sulphide it is reduced to sulphur. 3H20 ; 2S406”+60H’=3S20,”+2S0,”f3H20 ; 2S50,+60H’= E. H. R. The Preparation of Hydrogen Selenide from Metallic Selenides. L. MOSER and E. DOCTOR (2. anorg. Chem. 1921 118 284-292) .-The selenides of magnesium aluminium iron,INORGANIC CHEMISTRY. ii. 47 and zinc were prepared in a similar manner to the corresponding tellurides (this vol. ii 48) by passing selenium vapour over the heated metal in a vacuum.The aluminium and magnesium compounds were also prepared by direct combination of the metal with selenium in a crucible starting the reaction between the mixed components with a burning magnesium wire. All the products were considerably contaminated with metal except aluminium selenide which prepared by the latter process was practically pure. Aluminium selenide Al,Se forms a light brown powder unstable in air and magnesium selenide MgSe is very similar. Zinc selenide ZnSe is citron-yellow and iron selenide FeSe is black and metallic; both are stable in air. Hydrogen selenide was prepared in an apparatus similar to that used for hydrogen telluride by dropping the metallic selenide slowly into acid. The best results were obtained using aluminium or magnesium selenide.The gas was liquefied at the temperature of a solid carbon dioxide-ether mixture and by revaporisation was obtained pure. It is not decomposed by daylight in the liquid or gaseous form but is sensitive to ultra-violet light. Dry oxygen has no action on the dry gas but in presence of moisture decomposition is rapid. E. H. R. Selenious Acid and Heteropolyselenites. ARTHUR ROSEN- HEIM and LEONHARD KRAUSE (2. anorg. Chem. 1921 118 177- 192).-A large number of heteropolyselenites with vanadates and molybdates have been described by Prandtl and others (A. 1907 ii 477; 1912 ii 167; 1916 ii 333) who described numerous well- crystallised salts which however had variable compositions according to the conditions of preparation. These compounds have been re-examined with a view to determine whether they may not have a semi-colloidal constitution similar to that of the periodates (A.1919 ii 508). Experiments were first made to determine the state of aggregation of selenious acid in aqueous solution. Depression of the freezing point of water indicated slight association which has a tendency to decrease with time. The dissociation was determined by the hydrogen-ion concentration method and from the electrical conductivity the results obtained being 4.85. and 3.45. respectively. These results are taken to be consistent with the presence of associated (H,SeO,) mole- cules in solution. The method of estimating selenious acid by heating with potass- ium iodide and hydrochloric acid and distilling the iodine over into potassium iodide was improved by the addition of phosphoric acid to the hydrochloric acid.This prevents the formation of selenium iodide which may be the cause of low results. It was also found that selenious acid may be accurately titrated with sodium hydroxide; the best indicators are for the formation of NaHSeO p-nitrophenol and for complete neutralisation to Na,SeO thymolphthalein. Lithium selenite forms the hydrate 4Li,Se04,3H,0 ; ibs solubility has a negative temperature coefficient.ii. 48 ABSTRACTS OB CHEMICAL PAPERS. MoZybdoseZen~tes.-The composition of molybdoselenites was found to depend on the ratio of molybdate to selenious acid in the solution from which they were precipitated. When less than 1 mol. of selenium dioxide was present to 1 mol.of molybdate the potassium and barium salts corresponded with 2R20,2SeO2,5MoO,xH2O and the ammonium salt with 3(NH,),0,2Se0,,8M003,6H20. With more than 1 mol. of selenium dioxide per mol. of molybdate in solution salts were obtained in which the proportion of base was variable but the ratio SeO MOO was always very nearly 1 1. The ammonium salt 2(NH,),O,5Seb.,,5MoO3,8H2O white microscopic prisms was obtained by adding 15 mols. of selenium dioxide to a saturated solution of ammonium paramolybdate. K20,2Se0,,2M00,,3~5H20 forms microscopic prisms and the barium salt BaO ,2Se02,2Mo03,7H,0 a white crystalline precipitate. VunadioseZenites.-Vanadioselenious acid has the! composition 4SeO2,3V,Os 10H,O. An extensive series of experiments showed that as the concentration of selenious acid in the mother-liquor increased from zero to 5N the ratio of SeO to V,O in the solid phase increased from 4 3 to 5.5 3.Similar behaviour was shown by the ammonium vanadioselenites having the approximate formula 3(NH,),O 12Se0,,8V20,. It is concluded that the variable composition of the vanadic acid compounds is due to the formation of adsorption compounds although in the case of the molybdic acid compounds this is not no clearly demonstrated. The potassium salt E. H. R. The Preparation of Hydrogen Telluride from Metal Tellurides. L. MOSER and K. ERTL (2. anurg. Chem. 1921 118 269-283) .-A new method for preparing metal tellurides was devised which consisted in distilling tellurium at a low pressure (8 mm.) over the hot finely divided metal. In this way the tellurides of magnesium MgTe aluminium Al,Te iron FeTe and zinc ZnTe were prepared.The aluminium compound was obtained in an almost pure state; it is a blackish-brown lustrous amorphous substance decomposing in the air with formation of tellurium hydride. The other tellurides were all more or less contaminated with excess of the respective metal. Magnesium telluride forms a brown sintered mass iron telluride is grey and metallic and zinc telluride is pale brown. The last two are stable in air. For the preparation of hydrogen telluride a special apparatus was designed in which the powdered metallic telluride was dropped very gradually into acid in an atmosphere of nitrogen. Aluminium telluride proved the most suitable substance from which to generate the gas and hydrochloric acid the best acid to use.The yield of gas obtained under the best conditions was more than 80% of the theoretical. The gas was liquefied by passing through a tube immersed in a mixture of solid carbon dioxide and ether. In the liquid state hydrogen telluride is very sensitive both to daylight and ultra-violet light but the dry gas is quite stable in light. The dry gas is however immediately oxidised by oxygen. E. H. R.INORGANIC CHEMISTRY. ii. 49 The Preparation of Telluric Acid. JULIUS MEYER and HANNS MOLDENHAUER (2. anorg. Chern. 1921 119 132-134).- Telluric acid can be prepared in a pure state and in almost theoretical yield by oxidation of tellurium tetrachloride with chloric acid. Tellurium (10 grams) is boiled with 10 C.C.of nitric acid and 3 C.C. of hydrochloric acid until completely dissolved. To the hot solution is added gradually a concentrated solution of 9 grams of chloric acid and the solution is boiled until no more chlorine is evolved. A slight excess of chloric acid is added to avoid forma- tion of any explosible chlorine oxide. The solution is filtered through asbestos and concentrated by distillation in a vacuum on the water-bath thereby removing chlorine. The telluric acid can be crystallised out by the addition of concentrated nitric acid collected and finally freed from chlorine and nitrogen oxides by drying in a vacuum. It is obtained as a crystalline snow- white powder readily soluble in water having the composition H 6TeO 6. R. 0.E. DAVIS L. B. OLMSTEAD and F. 0. LUNDSTRUM ( J . Amer. Chem. SOC. 1921 43 1580-1583; cf. this vol. ii 56).-Vapour pressure curves have been constructed for the following solutions Ca(N0 ) 22*48% NH 19-18y0 H,O 58.34%; NaI 32-34y0 NH 16.062 H20 51.60% ; NH,*CNS 77.84y0 NH 22.16% ; NH,NO 33.7% NH 18+i2~0 H,O 47.48%; CaC1 12-9y0 NH 22.9y0 H,O 64.2%; Ca(N0,)2 55-8y0 NH 25-77y0 H,O 18.43%; NH 28.15% H,O 71.85%; NaI 64.88% NH 26.02% H,O 8.20% over the temperature range -16" to 40". It is shown that solutions of ammonium nitrate in ammonia and ammonium thiocyanate are very corrosive to iron and steel the calcium chloride-ammonia solution is less corrosive and calcium nitrate- ammonia and sodium iodide-ammonia solutions show no immediate corrosive action. Calcium nitrateammonia solutions seem to be the most promising of these solutions for practical use as an absorbent for ammonia in the synthetic ammonia process.The Action of Metals such as Copper and Zinc on an Aqueous Solution of Ammonium Nitrite. N. R. DHAR (2. anorg. Chem. 1921 119 176176).-The action of a solution containing ammonium nitrite on copper was attributed by Hof- mann and Buhk (A. 1921 ii 43) to the hydrolysis of the nitrite with formation of free nitrous acid. The observation that the metal is attacked even in presence of urea however renders this explanation improbable. Further solutions of other nitrites such as zinc nitrite which are hydrolysed as much as ammonium nitrite do not attack copper. The activity of the ammonium nitrite is probably related to its instability and ready decomposition into nitrous oxide and water. The Structure of Pyrophosphoric Acid.111. D. BALAREFF (2. anorg. Chem. 1921,118 123-130; cf. A. 1915 ii 446; 1917 ii 467).-In previous papers it has been shown that there is a good E. H. R. Vapour Pressures of Ammonia-Salt Solutions. J. F. S. E. H. R.ii. 50 ABSTRACTS OF CHEMICAL PAPERS. deal of evidence in favour of the unsymmetrical structure of pyro- phosphoric acid. The synthesis of the pyro-acid by combination of the ortho- and meta-acids in sulphuric acid would give added support to the hypothesis of an unsymmetrical structure but attempts in this direction were not successful even in acid con- taining 15% of free sulphuric anhydride. The change of colour of the salt NaAg,P,O from white to yellow on heating has been attributed to its decomposition into NaPO and Ag,PO but it is now shown that this does not occur the colour change being probably due to some physical change in the salt.No evidence as to the structure of the pyro-acid could be gained from a study of the dehydration of dihydrogen phosphates of alkali metals. The potassium salt heated a t 244" loses water and changes to the acid pyrophosphate K,H,P,O,; the rubidium salt behaves in the same way. The sodium salt loses water very slowly at 180" and in the course of about one hundred and seventy-eight hours becomes completely converted into Na,H,P,O,. The products of further dehydration a t a higher temperature depend on the water vapour pressure. In moist air a t 305" only soluble meta- phosphate is formed whilst in dry air at 330" about 75% of the metaphosphate formed is insoluble.Phosphoryl bromide dehydrates orthophosphoric acid to pyrophosphoric acid but not to the meta-acid. The action is a complex one and depends on the temperature and proportions of the interacting substances. A dilute solution of an alkali pyrophosphate after prolonged boiling shows the presence of orthophosphate proving that hydra- tion occurs slowly. E. H. R. Iso- and Heteropoly-acids. XVII. Polyborates in Aqueous Solution. ARTHUR ROSENHEIM and FELIX LEYSER (2. anorg. Chem. 1921,119 1-38).-An attempt was made to prepare simple and complex polyborates wit,h the object of comparing these with salts of other acids such as telluric antimonic periodic plumbic and stannic acids which show semi-colloidal properties.Methods for the quantitative estimation of boric acid were examined. The polarimetric method depending on the influence of boric acid on the optical rotation of tartaric acid is of limited application on account of the disturbing influence of salts or other substances present in solution. Titration with sodium hydroxide in presence of mannitol using phenolphthalein as indicator gives trustworthy results. Free boric acid in the presence of borate can be detected by boiling a sample of the substance for some minutes with dry acetone filtering evaporating the filtrate on a watch glass moisten- ing with a few drops of methyl alcohol and igniting when the characteristic flame coloration is given if free boric acid is present.An investigation of the equilibrium in the system Na,O-B,O,- H20 a t 0" confirmed the existence of the three salts Na20,B20,,8H,0 Na20,2B20,,10H20 and Na20,5B20,,10H20. Sodium penta- borate can readily be crystallised from solutions containing Na,OINORGANIC CHEMISTRY. ii. 51 and B,O in the ratio 1 5 but sometimes only crystalrJ of borax are obtained probably because the pentaborate is metastable a t ordinary temperatures and borax is the less soluble salt. Potassium pentaborate K20,5B20,,8H,0 is a well-defined characteristic salt separating from solutions in which the ratio B,O, KOH is 3 1 or higher. Its solubility is very low not much greater than that of potassium perchlorate. Potassium monoborate crystallises with 8H20 a t O" with 2.5H20 a t 30". Rubidium pentaborate is very similar to the potassium salt but crystallises with 10H,O.Thallium pentaborate like the potassium salt crystallises with 8H20 but is more soluble than the latter. Guanidine forms a diborate crystallising in elongated prisms with 48,o and a penta- borate with 8H20. Experiments on the dehydration of pentaborates showed that in the general formula R20,5B20p,xH20 two molecules of water are probably constitutively combined. Conductivity experiments indicated that in dilute aqueous solution the pentaborate anion is hydrolysed into the diborate anion and boric acid. I n presence of great excess,of boric acid this hydrolysis is prevented and the specific conductivity of sodium pentaborate a t 0" appears to be 85% of that of sodium diborate. Experiments on the hydrogen- ion concentration of solutions containing varying ratios of NaOH to B2.03 confirm the existence of a pentaborate ion in concentrated solution.The pentaborate ion appears to form complex anions with a number of metals. Whilst borax solution immediately precipitates zinc or cadmium hydroxide from a solution of a salt of the metal sodium pentaborate does not. Cobaltous hydroxide dissolves in sodium pentaborate solution to form a red solution in which although alkalis do not readily precipitate it the cobalt is in the kation. When this solution is oxidised with hydrogen peroxide however some cobaltic oxide is precipitated and a yellow solution is formed containing a complex cobalt anion. Nickel chromium (Cr"') manganese (Mn") and copper also appear to form complex anions. A very small quantity of a copper compound was isolated having approximately the composition 2Na,0,4C~0,12B,0~,50H,O.E. H. R. The Atomic Weight of Carbon. E. MOLES (Anal. Pis. Quim. 1921 19 255-259).-The value 12-005 for the atomic weight of carbon given by Richards and Hoover (A. 1915 ii 96) is held to be based on an erroneous value for the atomic weight of sodium. The value 12.000 is claimed to be more exact. G . W. R. The Oxidising Properties of Carbon Suspensions. F. FEIGL (2. anorg. Chem. 1921 119 305-309).-The oxidising effect of blood charcoal was studied in a qualitative manner by boiling solutions of different oxidisable substances with a sus- pension of the charcoal. I n acid solution hydrogen sulphide was oxidised to sulphuric acid potassium iodide to iodine mercurous salts to mercuric oxalic acid to carbon dioxide.I n alkaline solu-ii. 52 ABSTRAaTS OF UHEMICAL PAPERS. tion potassium iodide was oxidised to iodate alkaline sulphidea and sulphites t o sulphate cuprous and cupric sulphides to copper sulphate cobalt sulphide to sulphate potassium chromite to chromate. Sodium thiosulphate was unacted on in alkaline or neutral solution and sodium nitrite was unaffected in alkaline solution. A quantitative study of the oxidation of tervalent chromium to chromate was made after a method had been devised for removing from the solution a product formed by the interaction of the charcoal and potassium hydroxide which liberates iodine from potassium iodide. This was accomplished by boiling with potassium permanganate and removing the excess with hydrogen peroxide.The experiments showed that the proportion of chromate formed increased with the proportion of charcoal used but that with a constant quantity of charcoal the amount of chromate formed increased with the quantity of chromium salt taken. Different charcoals varied widely in their oxidising power but the differences seemed to bear no relation to the ash content. E. H. R. Aqueous Carbonic Acid Solutions. E. WILRE (2. anorg. Chem. 1921 119 365-379).-The dissociation constant of carbon dioxide solutions was measured by the conductivity method using a solution through which the gas was being continuously circulated. When an ordinary saturated solution was used without circulation the conductivity was found to increase during measurement probably through electrolytic changes caused by the current.Even with the greatest precautions variable results were obtained confirming the observations of earlier workers. It was observed that by contact with the metal electrodes (gold) even without passage of current the conductivity gradually increased. In three hours the dissociation constant K . lo7 increased from 3.07 to 4.5. Light seemed to have an effect in the same direction. E'or measur- ing the hydrogen-ion concentration a special hydrogen electrode was used consisting of a palladium capillary into which hydrogen was forced a t a pressure of 20 atm. The hydrogen-ion concentration was determined in presence of sodium potassium and barium chloride.In these solutions carbon dioxide has the character of a strong acid increasing with the concentration of salt. The hydrogen-ion concentration increases more rapidly than the total carbon dioxide concentration. The observations can be explained on the assumption that a solution of carbon dioxide in water contains orthocarbonic acid H,CO which containing no ketonic oxygen is a very weak acid. In concentrated salt solutions it is dehydrated to form the strong acid CO(OH),. Behaviour of Amorphous Carbon and Sulphur at High Temperatures. Carbon Sulphides. J. P. WIBAUT (Proc. K . A h d . Wetensch. Amsterdam 192 1 24 92-101) .-The action of sulphur on amorphous carbon a t high temperatures has been investigated. Pure sugar charcoal has been heated with sulphur a t temperatures from 400" to 1000" under reduced pressure for E.H. R.INORGIANICl CHEMISTRY. ii. 53 prolonged periods of time. A slow evolution of hydrogen sulphide due to the amall amount of hydrogen present in the carbon is observed and a carbon-like substance containing 1*98y0 of sulphur obtained. This subsfance yields no sulphur to toluene even after prolonged boiling and the residue after this treatment contained 2°03y0 of sulphur. Prolonged heating in a vacuum a t temperatures up to 1010" did not reduce the sulphur content nor was any volatile compound obtained. Prolonged shaking with bromine water oxidised 9% of the sulphur to sulphuric acid and heating in a current of hydrogen at temperatures up to 750" removes 77% of the sulphur as hydrogen sulphide; this reaction is exceedingly slow and must be regarded as an action between a sulphur com- pound and hydrogen and not as an action between hydrogen and sulphur vapour.This was further proved by the fact that heating in nitrogen did not reduce the sulphur content. The author con- siders that a solid carbon sulphide is formed which bears a strong resemblance to coal coke (cf. Stock and Praetorius A. 1913 ii 46). A further sulphide containing 3.5% of sulphur has been obtained by heating carbon purified by chlorine with sulphur. This substance has similar properties to the compound containing 2-0y0 of sulphur. Tho Deviations from the Gas Laws of Carbon Disulphide. ALFRED SCHULZE (2. anorg. Chem. 1921,118,223-230).-A number of observations on the properties of carbon disulphide vapour indicate that it is associated to a small extent.The increase of pressure observed when carbon disulphide and ether vapours are mixed a t constant volume at 80" under atmospheric pressure indi- cates association of the former to the extent of o.14y0 whilst vapour density determinations by Dumas's method give results corresponding with 2 yo association. Compressibility experiments at 80" showed @5y0 more association a t 2 atmospheres than a t 1 atmosphere pressure. The PV curves at 78-82' and 130.48" show that the amount of association decreases with increasing tempera- ture but a t constant temperature increases with increasing pressure. It is probable that in the liquid phase association is more con- siderable. E. H. R. J. F. S. New Theory of the Constitution of Hydroxides particu- larly those of the Basic Metallic Oxides.FR. TIEMANN (Chem. Zeit. 1921 45 1125).-To furnish an explanation for a number of phenomena in organic inorganic and electrolytic pro- cesses which are not in consonance with existing ideas the author proposes a new theory of the constitution of the hydroxides of the pronounced electropositive metals. It is suggested that these compounds do not contain hydroxyl groups but are to be regarded merely as true hydrates of the corresponding oxides that is to say that sodium and calcium hydroxides for example are not correctly represented by the formulze NaOH and Ca(OH)2 but are actually Na20,H20 and CaO,H,O a molecule of water being closely associated with the metallic oxide rJimilarly to the " water ofii 54 ABSTRACTS OF CHEMICAL PAPERS crystallisation " of salts.This applies to all the elements of groups I and I1 of the periodic system whilst the constitution of the hydroxides of those of groups I11 and IV (aluminium zinc) will depend on the electrochemical conditions under which they are produced. Only the hydroxides of the metalloids and non-metals are to be regarded invariably as true hydroxyl derivatives. With increasing basicity of the oxides the associated water molecules become increasingly firmly bound exactly as in the case of the increasingly basic character of salts containing associated water. So the dehydration of the hydroxides of calcium strontium and barium is effected with increasing difficulty in the order named. The sucrosates are cited to illustrate the application of the theory.If calcium hydroxide is regarded as a hydroxyl compound the chemical character of sucrose or dextrose is quite incompatible with the idea of a " neutralisation " of hydroxide looked on as a generator of hydroxyl ions. There can therefore only be a question of the displacement of the associated water by the sugar and the sucrosates must be formulated C1,H,,O 11 ,2CaO C ,H 120.G ,CaO etc. The isomerism of the hydroxides of tin and aluminium is also explained by reference to the theory e. g. AI(OH) and A4120,,H20+2H20 can both exist as individual substances and either one or the other will be produced according to the conditions of the reaction. The non-appearance of hydrogen peroxide de- rived from the union of two hydroxyl groups during electrolysis of a metallic hydroxide is explained by the new theory as due to the absence of hydroxyl groups.The electrolysis actually is that of say Na,O,H,O the associated water taking no part in thc process. There takes place simply a direct fission into metlal and oxygen which are liberated a t their respective poles. An assump- tion of the appearance of hydroxyl ions in any electrolytic process is quite unjust'ified. G. F. M. Preparation of Alcoholic Potassium Hydroxide Volumetric Solution. S. 3'. MCCALLUM ( J . Ind. E72g. Chein. 1921 13 943).-A solution which does not darken in colour when kept is prepared by dissolving potassium hydroxide in methyl alcohol (purified mood spirit) ; the solution must be filtered through glass- wool to remove insoluble potassium carbonatc etc.before it is used. 1 . P. s. Existence of Tetra-hydrated Sodium Sulphate in Mixed Crystals with Sodium Chromate. THEODORE W. RICHARDS and W. RUELL MELDRUM ( J . Amer. C h m . Xoc. 1921 43 1543- 1545).-lt is shown that crystals of the tetrahydrate of sodium chromate Na2Cr0,,4€I,O dissolve sodium sulphate as Na2S0,,4H,0 a form of sodium sulphate otherwise unknown to the extent of somewhat less than half the quantity corresponding with the same weight of sodium chromate in the supernatant liquid. When sodium sulphate was in largc excess no crystallisation could be induced by " seeding " the saturated mixture with the crystals of the mixed tetrahydrate above the transition temperature oE sodiumINORGANIC CHEMISTRY.ii. 55 sulphate and below this temperature only crystals of the deca- hydrate could be formed. Thus under these conditions the tetra- hydrate is so much more soluble than the phases containing more sodium sulphate as to be incapable even of metastable existence. J. F. S. Ammonium Radicles. 111. Ammonium. HANS HETNRICH SCHLUBACH and FRITZ BALLAUF (Bey. 1921 54 [B] 2825-2834; cf. A. 1920 i 822 and this vol. i 16).-The authors' experience with tetraethylammonium leads them to expect that the ammonium radicle would be extremely sensitive to rise in temperature and that there is no hope of isolating it by the electrolyses of solutions of ammonium salts in liquid ammonia on account of the impos- sibility o€ avoiding the thermal effect of the current and that the only prospect of success lies in displacement reactions effected a t a low temperature.They find that when well-cooled ammonium chloride is added to a solution of potassium in liquid ammonia a t -70" in the apparatus described previously for the preparation of tetraethylammonium decolorisation of the solution takes place before the calculated volume of hydrogen has been evolved the deficit amounting to as much as 65%; according to Moissan the whole of the hydrogen is evolved by the time the solution becomes colourless. The deficit cannot be attributed to the solubility of hydrogen in liquid ammonia since this is shown to be too small to account for the observed effect and it appears therefore that colourless ammonium is actually present in the solution. This conclusion is supported by the observation that the remainder of the hydrogen is evolved rapidly when the solution is cautiously warmed a t about -40".Repetition of Moissan's experiment shows that the non-observation of the production of ammonium is due to operatioil in too concentrated solution and consequent decomposition of the radicle by the heat liberated during the reaction. When a solution of potassium (14%) is added to a solution of ammonium chloride (1%) in liquid ammonia a t -70° a violent reaction is observed and each drop of added solution is immediately decolorised formation of ammonium and its con- version into the colourless form appearing to occur instantaneously ; tetraethylammonium and ammonium therefore stand to one another in the same relationship as triphenylmethyl to methyl.In spite of the violence of the reaction the yields of ammonium by this method are good and readily reach 50% ; the influence of concentration is however again apparent and it is to be expected that an improvement in yield would bc observed with more dilute solutions. The behaviour of ammonium towards the reagents used with tetraethylammonium is described. Corresponding with the rapid isomerisation to the colourless form the equilibrium is here greatly displaced in the direction of the latter and it is probable that dissociation and consequent reaction only occur in close proximity to the temperature of decomposition. A reaction with dimethyl- pyrone could not be observed. Iodine on the other hand appears3. 56 ABSTRACTS OF CHEMICAL PAPERS.to react immediately with ammonium but the quantitative examination of this change could not be completed on account of the experimental difficulties involved. Vapour Pressure of the System Lithium Nitrate Ammonia. R. 0. E. DAVIS L. B. OLMSTEAD and F. 0. LUNDSTRUM ( J . Amer. Chem. Xoc. 1921 43 1575-1580).-The solution of ammonia in lithium nitrate has been studied with the object of finding an absorbent for ammonia in the synthetic production of this gas. The use of ammonium nitrate (Kurilov A. 1898 ii 156) and ammonium thiocyanate (Foote and Hunter A 1920 ii 246) suffers from the serious drawback that the liquids produced when these salts adsorb ammonia attack metals rapidly. A large number of salts have been tested as to their suitability for this purpose and of these lithium nitrate alone forms a liquid with ammonia in the absence of water whilst calcium nitrate tetrahydrate liquefies in the presence of a little water.The ammonia contained in 1 C.C. of the lithium nitrate solution saturated a t 24" is equivalent to 26.0 C.C. of 0.95N sulphuric acid whilst that for the calcium nitrate solution under identical conditions is 18.5 C.C. of 0.95N acid. Vapour pressure measurements have been made for the solution 36.34y0 ammonia 63.66% lithium nitrate and for several other mixtures containing 6.06-58-66~0 of water. The solutions of ammonia in lithium nitrate have no action on machine steel iron wire and nichrome wire after several months' contact but nickel steel shows a slight action after several months. The results show that a solution of lithium nitrate in ammonia with a small percentage of water should be a good absorbent for the removal of ammonia from mixtures of nitrogen hydrogen and ammonia.The absorption could be effected at 0" and a large proportion of the ammonia released either by a small increase of temperature or by reduction of the pressure. J. F. S. GEOFFREY ISHERWOOD HIGSON (T. 1921,119 2048-2055). J. H. REEDY ( J . Amer. Ohem. Xoc. 1921 43 1440-1445).-1n an earlier paper (A. 1915 ii 733) it was shown that the electrode Ag IAgBrO,! O*lNKBrO only reached a steady value (0.631 volt) after being kept for five days if the bromate was prepared by the action of bromine on silver nitrate solution but if it was obtained by double decomposition of silver nitrate and potassium bromate the correct value was a t once obtained.Investigation now shows that silver bromate is dimorphous existing as tetragonal bi-pyramids and as hair-like crystals. The tetragonal crystals are stable at temperatures below 98.5" (the transition point) and the fine hair-like crystals are stable above this temperature. Difference of solubility of the two forms explains the irregular behaviour of the electrode mentioned above. The solubility of silver bromate has been determined a t temperatures from 25" to 90" and the following values have been found 25" 0.196 ; 35" 0.269 ; 45" 0.371 ; 55" 0.497 ; 65" 0.648 ; 75" 0.832 ; 85" 1.055 H. W. The Reaction between Persulphates and Silver. Silver Bromate.INORGANIC CHEMISTRY. ii. 57 and go" 1.325 the solubilities being expressed in grams per 100 grams of water.The solubility curve indicates 98.5" as the transi- tion temperature a value which is confirmed by a dilatometric measurement of this quantity. Dry silver bromate melts a t 308-310" and is stable toward heat and light but in the presence of water it darkens slowly a t the ordinary temperature and rapidly a t high temperatures. If a little impurity such as dust is intro- duced into heated silver bromate decomposition occurs with explosive violence. Silver bromate crystals absorb a considerable quantity of air which is slowly evolved a t high temperatures. It is shown that silver bromate may be used as a standard in iodo- metry. The method of use consists in placing 1 gram of bromate with an excess of potassium iodide in 150 C.C.of water in a 250 C.C. flask ; this is heated on a water-bath to effect double decomposition. The contents of the flask are cooled and made up to 250 C.C. Samples of 25 C.C. are withdrawn acidified with dilute hydrochloric acid and titrated with sodium thiosulphate. Arsenious oxide gives a result about 0.3% higher than silver bromate but after recrystal- lising the arsenious oxide from hydrochloric acid this figure was reduced to 0.05y0. This indicates that whilst silver bromate may have a somewhat higher oxygen equivalent than arsenious oxide this defect is fully compensated by its greater definiteness. J. P. S. Alkali Silver Thiosulphates and their Ability to Add Ammonia. ERIK JONSSON (Ber. 1921 54 [B] 2556-2564).- Additive compounds of alkali silver thiosulphate and ammonia have been described previously by Schwicker (A.1889 942) and by Meyer and Eggeling (A. 1907 ii 347) who however do not record analyses of their products. A repetition of their work has given somewhat different results. The ability to form additive cornpounds seems to depend on the presence of unused subsidiary valencies of the silver atom and is most marked in compounds of the type K,S,O,,Ag,S,O,; it is scarcely noticeable in the case of the salts 2M,S,03,Ag,S,0 and 5M2S,0?,3Ag2S,0,. The existence of colourless and yellow alkali silver thiosulphates (cf. Meyer and Eggeling Zoc. cit.) is confirmed but it appears doubtful whether their isomerism is explicable by assigning the respective formulix AgS*SO,*OK and KS*SO,*OAg since their behaviour towards ethyl iodide indicates that the silver is attached to the sulphur atom in each case. Conversion of the colourless into the yellow modification can be effected frequently by cautious warming with water but too drastic treatment leads to tjhe formation of silver sulphide sulphur dioxide and sulphate.It appears therefore that the yellow compounds are intermediate products in the decomposition of the colourless salts and the transformation is possibly explained by such a scheme as KO*SO,*SAg + MO*S*SO,*.Ag. The following individual substances are described the saZt 2K,S203,Ag,S,03 colourless prisms from silver nitrate and potassium thiosulphate in the presence of ammonia; the salt 5KzSz0,,3Ag,S,0 long colourless prisms ; the compound 3KAgf$0,,NH3,2H,0ii.58 ABSTRACTS OF CHEMICAL PAPERS (cf. Schwicker loc. cit. who regards it as KAgS,O,,NH,) colour- less plates which are converted by warm dilute ammonia and into a yellow salt of the same composition and are transformed by warm water into the compound KAgS203 1.5H20 colourless needles and KAgS203 .yellow hexagonal pyramids ; the salt 2NaAgS,0,,3H20 small irregular plates ; the salt 5(NH4)2%03 3 3&2S@3 long prisms and the compound (NH4)AgS20 prismatic crystals (by the action of ammonium thiosulphate on a solution of silver oxide in ammonia) ; the salt 5Rb,S20p,3Ag,S203 colourless prisms (cf. Meyer and Eggeling Zoc. cit.) which is transformed by warm water into the salt 3RbzS20,,4Ag2S2O3,. yellow prisms ; the salt 3RbAgS20,,NH,,2H,0 (Meyer and Eggehng record the unstable yellow salt Ag,S,03,3NH3,H20. RbzS203,Ag2S203,NH,) ; H.W. Metallic Hydrides. 11. Hydrides of the Alkaline-earth Metals and of Lithium. FRITZ EPHRAIM and EDUARD MICHEL (Helv. Chim. Acta 1921 4 900-924; cf. A. 1921 ii 638).-The preparation of the hydrides and the measurement of their dissociation tensions is recorded. When attempts are made to compare the tensions of the different hydrides with one another it becomes apparent that all measure- ment of dissociation pressure of the alkali and alkaline-earth hydrides are vitiated by the use of impure material containing a greater or less proportion of dissolved metal which tends to depress the tension. Within each group the effect of the metal increases with its atomic weight and the influence of sublimation lies in the same direction.In the cases of caesium and barium hydrides these actions render the measurement of dissociation pressures a t high temperatures almost impossible. The influence of the atomic weight of the metal on the stability of the alkali hydride cannot be regarded as elucidated completely but the authors consider from their own experiments that a slight diminution of stability with increasing atomic weight of the metal is probable. The tension curves of lithium hydride could not be measured sincc a material which would withstand the chemical action of the hydride and metal could not be found. It is however established that it is the most stable of all the alkali or alkaline-earth hydrides which is in accordance with its great heat of formahion.Calcium hydride appears to be more stable than barium hydride whilst thc strontium compound occupies an intermediate position. The behaviour of the alkali and alkaline-earth metals towards hydrogen is not confined to the formation of hydrides XH and XH but extends also to the production of solutions the phenomenon being more marked with the hydrides of the alkaline earths than with those of the alkalis. The absorption of hydrogen occurs previously to and in part simultaneously with the formation of the hydrides; this occurs to a greater extent with tlhe alkaline earth than with the alkali metals. The formation of hydrides occurs slowly with the alkali metals,MORQANIC CHEMISTRY. ii. 59 rapidly and with incandescence in the cases of the alkaline-earth metals.This appears to be due to the greater solubility of the hydride in the metal. The same explanation applies to the ob- servation that calcium hydride for example can be formed a t a temperature which is certainly considerably higher than the tem- perature of dissociation of the pure hydride. The liquid nature of the alkali hydrides a t the temperature of their formation con- tributes also to the slowness of absorption of hydrogen since the eutectic mass protects the metal from further action. Investigation of the hydrides of lanthanum and cerium (Math- mann and Baur A 1903 ii 213) and of neodymium and praseo- dymium (Mut'hmann and Beck A. 1904 ii 409) have given results similar to those now observed with the alkaline-earth metals except that the displacement of the tension due to the presence of an excess of metal is even more considerable.The increase in the action of an excess of metal with increasing atomic weight is there- fore apparent not only within a group in the periodic system but also from left to right with increasing valency of the metal. H. W. The Discovery of an Equilibrium between Cement and Lime-water. RICHARD LORENZ and GUSTAV HAEGERMANN (2. anorg. Chem. 1921 118 193-201) .-When finely-ground Port- land cement which has been previously treated with water and dried is stirred with a fixed quantity of water in absence of air the quantity of lime taken up by the water eventually reaches a maximum value. This maximuin is much less than the solubility of lime in water and depends on the quantity of cement present in proportion to the water and also to some extent on the fine- ness of the particles.The existence of this maximum is shown to depend on the partition coefficient of lime between the water and the silica-alumina gel formed by the decomposition of the cement constituents such as monocalcium silicate and tricalcium aluminate. This partition coefficient was determined by repeatedly treating the cement with fresh water until the whole of it had decomposed The ratio of lime in the solid phase to lime in the water was then found to be about 7.0. The existence of the partition coefficient shows that no definite compound is formed between the lime and the constituents of the gel. [See also .I. 8oc. Chem. Ind. 1922 1 5 ~ . ] E. H. R.The Solubility of Glucinum Sulphate in Water and Sul- phuric Acid at 25". HTJBERT THOMAS STANLEY BRITTON (T. WILHELM BILTZ and GUSTAV F. HUTTIC (2. anorg. Chem. 1921 119 115-131).- For the investigation of the ammoniates of magnesium haloids special precautions were taken in the preparation of pure mag- nesium chloride bromide and iodide. Ephraim's results (A. 1912 ii 546) which were not confirmed were probably due to the fact that his magnesium chloride contained basic salts. The 1921 119 1967-1971). Ammoniates of Magnesium Haloids.ii. 6Q ABSTRACTS OF CHEMICAL PAPERS. hexammoniate of magnesium chloride is formed in about fifteen hours a t room temperature when pure magnesium chloride is saturated with ammonia and the product is extraordinarily voluminous.Magnesium bromide behaves similarly but in the case of the iodide the increase in volume when the hexammoniate is formed is relatively slight. Observations were made on the time taken for the vapour pressure to become steady with different proportions of ammonia in the solid phase. From these observ- ations definite rules can be formulated regarding heterogeneous equilibrium in a solid-gas system. When two non-miscible sub- stances are present in the solid phase equilibrium is reached with gradually diminishing velocity usually in the course of a few hours depending on the temperature and the nature of the sub- stances. When one constituent just disappears for instance from a mixture containing principally a lower ammoniate and a small quantity of a higher ammoniate equilibrium is attained very rapidly.When unsaturated mixed crystals are present for example of two ammoniates equilibrium is reached very slowly often requiring several days. This case occurs with the magnesium haloids containing 5.5 to 5.8 mols. of ammonia. When the ammonia content is very nearly 6 mols. addition of a very small quantity of ammonia even a few hundredths of a mol. causes a very rapid rise in vapour pressure equilibrium being rapidly attained. On account of this the dissociation pressures of the hexammoniates could not be accurately determined. These ammoniates may be compared with the zeolites which unlike normal hydrates lose water very rapidly. The phenomenon has not been observed with other ammoniates. Magnesium chloride and bromide both form a diarnmoniate and a monoammoniate; the iodide forms only a diarnmoniatc.The table gives the heats of formation in Cals. and the absolute tem- peratures a t which the dissociation pressure is 100 mm. Saturated mixed crystals. 2NH,. lNH,. 17-2 ; 475" 38.7 ; 636" - MgC1 13.3; 367" 17.9; 495" 20.8; 573" MgBr 15.2 ; 420' 20.1 ; 559' 21.7 ; 606" MgI2 E. H. R. The Solidification Diagram of the Zinc-Arsenic Alloys. W. HEIKE (2. u w g . Chem. 1921 118 26&268).-Thermal examination was made of alloys containing from 6.6 to 92% of arsenic and with the aid of the results the equilibrium diagram was constructed. Two compounds both melting without decom- position are formed ZngAs2 m p. 1016" and ZnAs2 m. p. 771"; the former has a transition point a t 671". With excess of zinc pure zinc appears with Zn3As2 no solid solutions being formed.Arsenic dissolves little zinc but on the other hand is soluble to a considerable extent in the compound ZnAs,. Two eutectics are formed at 62% and Sl*5y0 As respectively the corresponding tem- peratures being 730" and 723". Both compounds -are,very brittle,INORGANIC CHEMISTRY. ii. 61 and ZnAs shows a well-marked cleavage. shows super-cooling during crystallisation of the alloys. This compound always E. H. R. The Fusion Diagram of Cd(N0,),,4H20+Ca(N0,),,4H,0 at Pressures of 1 to 3000 kilo. /cm.2. MEINHARD HASSELRLATT (Z. anorg. Chem. 1921 119 313-324).-The fusion diagram of the system Cd(N03),,4H,0+ Ca(NO3),,4H2O a t the normal pressure has been previously determined (A. 1913 ii 484).It was shown that the stable form of calcium nitrate forms a eutectic with cad- mium nitrate at 91% Ca(N0,),,4H20 and 40.6" whilst the unstable form of the calcium salt forms a continuous series of mixed crystals with the cadmium salt. The effect of increased pressure up to 3000 kilos. per sq. cm. on the diagram has now been investigated. The general form of the diagram is unchanged. The p-t curve for mixed crystals containing a high proportion of the calcium salt could not be followed at higher pressures on account of the rapid change of the calcium salt into the stable form. Excess of the cadmium salt inhibits this change but as the pressure increases more cadmium salt is needed t o produce this effect. With in- creasing pressure the m. p. of the stable calcium salt rises much more rapidly than that of the unstable.The latter does not form mixed crystals with cadmium nitrate. The lowering of the m. p. of the stable calcium salt by the cadmium salt is independent of the pressure. With increasing pressure the eutectic point moves towards the cadmium side; at 1000 kilo./cm.2 it is at 79% calcium nitrate 47%" ; at 2000 kilo./cm.2 74% and 55" and at 3000 kilo./cm.2 71% calcium nitrate and 61.5". E. H. R. Light Reactions of the Oxides of Titanium Cerium and the Earth Acids. CARL RENZ (Ndv. Chim. Ada 1921 4 961- 968; cf. A. 1921 ii 316).-!I'itanium dioxide cerium dioxide niobium pentoxide and tantalum pentoxide are in themselves stable towards light but become markedly photosensitive in the presence of suitable media. Reaction is due to reduction; this is the more remarkable since the oxides are reducible by purely chemical means with considerable difficulty.Titanium dioxide niobium pentoxide and to a less degree cerium dioxide undergo reduction when exposed to light in the presence of certain organic liquids and reducing solutions par- ticularly glycerol. A lower oxide appears to be formed (zirconium dioxide is not photosensitive and does not form a lower oxide) which on exposure to air or on being heated regenerates the original material. In the case of niobium pentoxide the process depends to some extent on the presence of impurities notably stannic and tungstic acids zirconium compounds and titanic acid or its anhydrides. Brown vanadium pentoxide becomes black with greater or less rapidity when exposed to light beneath glycerol benzaldehyde cinnamaldehyde cuminol or aqueous mannitol solu- tion; a lower oxide initially vanadium tetroxide is produced.Solutions of citric or tartaric acid in absolute alcohol become greenii. 62 ABSTRACTS OF CHEMICAL PAPERS. and ultimately blue when illuminated in the presence of vanadium pentoxide ; carbon dioxide is evolved freely. Similar decomposition is observed with mandelic acid but in this instance the vanadium pentoxide is blackened. Brown neodymium oxide containing praseodymium does not alter in appearance when illuminated under glycerol or phenylhydrazine ; it becomes bluish-grey when warmed with the latter owing to conversion of the brown to the yellow oxide of praseodymium. When exposed to sunlight in the presence of glycerol benzaldehyde or tartaric acid dissolved in alcohol bismuth oxide becomes grey and ultimately dark black.Reduction to the lower oxide and possibly to the metal Cakes place. I n similar circumstances antimony trioxide is also photosensitive. H. W. Concentration of the Erbium Earths. PAUL H. M-P. BRINTON and C. JAMES ( J . Amer. Chem. SOC. 1921 43 1397- 1401).-Four methods for the concentration of t'he less basic of the rare earths have been investigated ; the methods examined are (1) formation of basic nitrates (2) crystallisation of chlorides from 1 1-hydrochloric acid (3) formation of basic chlorides and (4) formation of basic thiosulphates. The authors highly recom- mend the first method for the separation of erbium holmium dysprosium and the less basic earths from yttrium and the second method for the separation of holmium and dysprosium from yttrium.The basic nitrate formation was carried out with (a) a solution of yttrium nitrate containing a little erbium and ( 6 ) a yttrium-erbium-holmium mixture. I n the former case the solution was boiled and treated with a fairly concentrated solution of sodium hydroxide and thoroughly boiled. The yttrium hydroxide which first precipitated soon dissolved. The addition of sodium hydroxide was continued until minute crystals of the basic nitrate were observed swirling through the liquid. The whole was then set aside to cool when a mass of needle-like crystals of the basic nitrate was obtained. These were collected dis- solved in the least amount of nitric acid and treated with sodium hydroxide solution as before.The basic nitrate crystals from this when dissolved in nitric acid gave a rose-red solut)ion which exhibited intense absorption bands of erbium thus showing that the erbium was rapidly collecting in this frackion. The original filtrate was treated several times with sodium hydroxide and although the concentration of nitrates was kept high the erbium absorption bands soon began t o fade. The results obtained with the second mixture were equally good. The cr~7stallisation of the chlorides was cff ccted with a solution containing yttrium holmium and dysprosium. The solutioii in hydrochloric acid was boiled down unt(i1 acid of constant boiling point was obtained. The solution was then evaporated until a scum appeared on the sur€ace when i t was set aside for fifteen to twenty hours.The crystals were separated by decantation and the crystallisation proceeded with; by the time the tail fraction had become No. 9 and the head fraction No. 4 owing to the combination of smallINORGANIC CHEMISTRY. ii. 63 head fractions it was found that the atomic weights had become 02.5 and 124.0 respectively. After four further fractionations the atomic weight of the tail fraction No. 12 was 91.5 whilst that df the head fraction No. 4 was 133.70. The order of separation in order of decreasing solubility of the chlorides is erbium yttrium holmium dysprosium. J. F. S. Disglomeration and Formation of the Autogenous Lead Tree. A. THIEL (Ber. 1921 54 [B] 2755-2758; cf.A. 1920 ii 622) .-Disglomeration which has been observed previously in thc cases of lead and copper is also exhibited by tin when the latter is preserved for some time under stannous chloride solution in a loosely stoppered bottle. Large uniform crystals of lead become strongly corroded when preserved for some weeks beneath Heller's solution ; a consider- able quantity of lead powder is formed but as expected there is no evidence of disglomeration that is formation of deep fissures a t the boundaries of the crystallites. Unexpectedly in the light of the previous theory the large crystallites readily exhibit the formation oE t'he lead tree when preserved beneath a solution of lead nitrate acidified with nitric acid. The phenomenon is observed only after the formation of a white skin of basic salt on the metal and is explained in the following manner.The presence of the skin inhibits the contact of dissolved lead salt and metal by con- vection and greatly impedes the diffusion of the lead ion. Beneath the skin therefore the solution soon cont'ains practically only lead nitrate and is poor in lead ions whereas the external solution still contains lead nitrate and therefore has a much higher lead ion concentration. The possibility of the formation of a short- circuited concentration cell is thus provided. H. W. The Chemical Behaviour of Crystallised Binary Com- pounds with one Component Nobler than Hydrogen. G. TAMMANN (2. anorg. Chem. 1921 118 93-104).-The author draws a comparison between metallic mixed crystal series and binary compounds.In the former case the members of a mixed crystal series behave chemically and electrically in a similar manner to one or other component according to the proportion of each present with sharply defined limits a t molecular fractions which are generally a simple multiple of 1/8. This behaviour is correlated with the lattice structure of the mixed crystals and may be expected also in crystallised binary compounds which have a similar lattice structure the difference being that in the latter case the proportions of the two kinds of atom are fixed. It is to bc expected that binary compounds will show similarity chemically or electrically to one or other component and when two or more compounds of the two elements are formed some will resemble one compoiicnt and some the other.As an example confirming this view the compounds of lead and palladium are cited. In this series the compounds Pb,Pd PbPd PbPd and PbPd have been identified. I n a solution of lead nitrate againstii. 64 ABSTRACTS OF CHEMICAL PAPERS. lead these all give a potential equal to that of palladium but as soon as any free lead is present the potential drops to zero. Chemically all the palladium-lead compounds are as resistant as palladium. Binary compounds can be conveniently classed as resistant or non-resistant the former showing the properties of the nobler the latter those of the baser component. The above principles are applied to the discussion of a large number of binary compounds principally metallic such as those present in alloys of gold silver copper and platinum besides sulphides silicides and carbides and it is shown that the com- pounds can be classified as resistant or non-resistant.The more base the inactive component is the greater is the number of atoms of the nobler component necessary to protect it. I n general a smaller number of gold than of silver atoms are needed to protect a given atom of a baser metal. These considerations apply to compounds in which one component is nobler than hydrogen. When both are less noble than hydrogen the classification into resistant and non-resistant does not apply since both constituents and their compounds decompose water. Apart from compounds of this type it is possible in a series of binary crystallised con- glomerates to determine from a few measurements of their galvanic potential which of the components they will resemble in their chemical character.E. H. R. The Chemical and Electrical Behaviour of some Series of Alloys WILHELM JENGE (2. anorg. Chem. 1921 118 105- 122).-With a view to test the theory put forward by Tammann (preceding abstract) that crystallised binary compounds when no hffusion of the atoms is possible may be expected to behave chemically and electrically as one or other of the constituent elements a number of series of alloys in which binary compounds are formed were examined. The alloys were used as anodes and subjected to the action of halogen sulphate or nitrate ions and were tested against acids and alkalis. In the cobalt-silicon series in which the compounds formed are Co,Si Co,Si CoSi CoSi CoSi those having less than 32% of silicon were readily attacked by acidic ions but those with higher silicon content were resistant. That is to say CoSi and the higher silicides behave as silicon the other compounds as cobalt.Towards cold acids the same compounds were respectively resistant and non-resistant and towards cold alkalis all were resistant except CoSi the behaviour of which resembled that of silicon. No sharp demarca- tion of properties was found in the behaviour of the alloys towards hot acids and alkalis because the cobalt loses its passivity and decomposes water. In the series of nickel-silicon alloys some- what similar results were obtained but the compound Nisi unlike CoSi was not resistant to halogen ions. I n the manganese- silicon series only Mn,Si was non-resistant to acids and all that is Mn,Si MnzSiy and MnSi were resistant to sodium hydroxide.Alloys of antimony with cadmium and tin and of bismuth with thallium were also examined. The compounds Cd3Sb and Zn3Sb,INORGANIC CHEMISTRY. ii. 65 have the potentials of cadmium and tin respectively whilst CdSb and ZnSb soon approximate to the hydrogen potential. The cadmium alloys precipitate antimony and lead from solution and Zn,Sb precipitates not only lead but also cadmium. A bismuth- thallium alloy with the composition Bi,TI gives the hydrogen potential but after etching with hydrochloric acid the bismuth potential indicating that the surface thallium atoms have been removed leaving only bismuth exposed. Of the lead-thallium alloys those with over 0.49 mol.of lead show the lead potential those with 0 to 0.475 mol. of lead show t'he thallium potential. Great difficulty was experienced in measuring the potentials of the alloys of magnesium with copper lead cadmium and tin but i t appears that at the moment of contact with the electrolyte they ha;; the magnesium potential which however rapidly fa&. E. H. R. Physical Chemistry of the Oxides of Lead 11. The Supposed Enantiotropy of Lead Monoxide. SAMUEL GLAS- STONE (T. 1921,119 1914-1927). Binary Systems of the Sulphates Chromates Molybdates and Tungstates of Lead. F. &!I. JAEGER and H. C. GERMS (2. anorg. Chem. 1921,119 145-173).-The paper comprises an account of thermal investigations of the binary systems of PbO with SO CrO MOO and WO respectively and of the different systems formed by pairs of the compounds PbSO PbCrO PbMoO and PbWO,.By an optical method the transition tem- perature of PbO from the red tetragonal low temperature form to the yellow rhombic high temperature modification was found to be 587". The melting point of pure lead oxide is 879". The following melting points were also freshly determined and differ slightly from accepted values chromium trioxide 198" ; molybdenum trioxide 795"; tungsten trioxide 1473". The examination of the binary systems formed by lead monoxide with the acid anhydrides was limited in each case to the partial system PbO-PbM"'0,. In the system PbO-PbSO the existence of the following compounds was recognised Bb4SO7 Pb,SO Pb,SO PbSO,. The f i s t has no real melting point but decomposes at 897" forming Pb,SO m.p. 961" which has a transition point at 450". Pb,SO (lanarkrite) has m. p. 977". PbSO decomposes markedly at 1135" and its m. p. is estimated by extrapolation to be 1170". The transition point of PbSO from the p to the low temperature a form is 864&1". Three eutectics are formed a t 89 mols. % PbO and 835" 60 mols. yo PbO and 950" and 34 mols. yo PbO and 960". I n the system PbO-PbCrO the compounds Pb,CrO Pb7Cr,01 Pb,CrO and PbCrO were recognised. The first has no real melting point and exists only below 815'. Pb,Cr201 m. p. 854" has a reversible transition point at 744" and forms with Pb,CrO m. p. 920" a eutectic at 68 mols. % PbO and 841'. Lead chromate PbCrO is found to be trimorphous; the a-form VOL.CXXII. ii. 3ii. 66 ABSTRACTS OF CHEMICAL PAPERS. is stable below 707"; the P-form between 707" and 783" and the y-form above 783" melting at about 844" with evolution of oxygen. The heat effect of the change CI p is small and is sharper in binary mixtures with lead oxide than in the pure substance. The eutectic between PbCrO and Pb,CrO occurs a t 820" but this part of the equilibrium diagram could not be determined accurately on account of decomposition. The system PbO-PbMoO shows only two compounds Pb,MoO m. p. 951" and PbMoO m. p. 1065". There are two eutectics a t 87.5 mols. % PbO 762" and a t 40 mols. yo PbO 933". The tungstates correspond with the molybdates Pb,WO m. p. 899" and PbWO m. p. 1123" with a transition point a t 877". The equilibrium diagram for the system PbCr0,-PbS04 is largely conjectural owing to the considerable amount of decompo- sition occurring a t higher temperatures.There is a gap in thc mixed crystal series between about 40% and 30% PbCrO,. Thc mixed crys\als have transition points a t 934" 874" and 748". In the PbS0,-PbMoO system mixed crystals are formed con- taining up to 6 mols. yo sulphate or 2 mols. yo molybdate. There is a eutectic a t 57 mols. yo molybdate and 962". Ah 879" the mixed crystals have a transition point. In the PbS0,-PbWO system the mixed crystals of the P-type separating a t the eutectic temperature contain respectively 37 mols. yo sulphate and 7 mols. Yo tungstate. The eutectic is at 51 mols. yo tungstate and 995". At 875" occurs the ~ZCI-sulphate transformation and a t 859" the corresponding tungstate change.The PbCr0,-PbMoO diagram is largely hypothetical. The composition of the limiting mixed crystals on the molybdate side is 48 mols. % PbCrO a t 838" the eutectic temperature. Transitions occur a t 799" of y-+P-chromate mixed crystals and a t 697" @-+a. In the PbCr0,-PbWO system the eutectic temperature is 837" and the limiting mixed crystals on t'he tungstate side contain 41 mols. :& PbCrO,. Lead molybdate and lead tungstate form an isodimor- phous mixed crystal series with a transition temperature a t 1082". A mixture containing 75 mols. yo PbMoO is in equilibrium a t this temperature with bot!h kinds of mixed crystal. Photochemistry of Thallous Chloride. 11. CARL Rmz (HeZv. Chirn. Acta 1921 4 950-960).-A continuation of previous work (A.1920 ii 71). Thoroughly illuminated blackish-brown thallous chloride in consequence of .photolysis contains as primary product more or less grey to slate-grey photothallous chlorides in addition to yellow intermediate thallous-thallic chlorides formed in accordance with the scheme 6TlC1-t- Light = photochloride+ TlC13,3T1C1. Thallic hydroxide formed by subsidiary actions is also present. These phases characterise the photo-processes in those cases in which the change of colour extends over the scale greyish-brown dark greyish-brown blackish-brown and hence occur when t'tlallous chloride is illuminated in the dry condition under water and in the presence of solutions of many neutral salts. In the presence of reducing agents or of organic hydroxy- E.H. R.INORGANIC CHEMISTRY. ii. 67 acids the action of light on thallous chloride only leads to the production of the photochloride. The formation of thallous- thallic chlorides is not observed in the presence of alkalis or alkali carbonates which decompose these compounds immediately. The production of photothallous chlorides and of thallic hydroxide does not occur in the presence of hydrochloric acid even without the addition of organic substances. Photothallous chloride can be prepared by purely chemical methods if ferrous sulphate is added to a boiling saturated aqueous solution of thallous chloride and the mixture is treated with an excess of ammonia. The black precipitate of photothallous chloride and iron hydroxides is allowed to settle and is subse quently washed with hydrochloric acid until the iron compounds are dissolved ; the slate-grey photothallous chloride so obtained behaves in exactly the same manner as the photosynthetic product. H.W. Ammoniates of Cupro- and Thallo-haloids. WILHELM BILTZ and WILHELM STOLLENWERK (2. anorg. Chem. 1921 119 97-1 14).-The formation and vapour pressures at different temperatures of ammoniates of cuprous and thallous chloride bromide and iodide were investigated using apparatus similar to that employed in experiments on the ammoniates of silver haloids (A. 1921 ii 201). When saturated with ammonia gas cuprous chloride first shrinks to a yellow mass then swells and becomes greyish-white. Saturation at -70" to -30" requires a t least a day. When the excess of ammonia is allowed to evaporate at room temperature and atmospheric pressure cuprous chloride triammoniate remains.I n damp air it quickly turns green. The pressure isotherms also indicate the existence of a sesqui- ammoniate and a monammoniate. Cuprous bromide behaves similarly forming a white triammoniate a sesquiammoniate and a monammoniate. Cuprous iodide absorbs ammonia quickly a t room temperature. It forms four compounds containing re- spectively 3 2 1 and Q mol. of ammonia. In the following table are given the heats of formation Q in Cals. and the temperatures in absolute degrees a t which the dissociation pressures of all these compounds are equal to 100 mm. 3NH3. 2NH,. 1 &NH3. lNH,. WH3. CuCl 9.48; 283" - 12-61; 326" 16.i3; 417.5' - CuBr 9.50; 283" - 13.15; 339" 14-64; 369.0' - CUI 10.37; 286-5" 11.30; 298" - 14.70; 371.0" 15.22; 390" Thallous haloids do not absorb ammonia a t the ordinary tem- perature but in liquid ammonia they all form triammoniates.The vapour pressures are all very close to those of ammonia itself. The triammoniates are soluble to a certain extent in liquid ammonia the solubility increasing with rising temperature and with the atomic weight of the halogen. The heat of formation is about 7.1 Cal. for the ammonia compound of each of the three haloids. No lower a,mmoniates are formed. E. H. R. 3-2ii. 68 ABSTRACTS OF CHEMICAL PAPERS. The Action of Molten Alkali Chlorides on Copper Oxide. J. ARVID HEDVALL and GUNNAR BOOBERG (2. anorg. Chem. 1921 119 213-216).-1t was shown in a former paper (Hedvall and Heuberger A.1921 ii 508) that potassium chloride could not be used as a flux in the fusion of cupric oxide with aluminium oxide on account of a reaction taking place between the potassium chloride and copper aluminate. It is now shown that when copper oxide is heated with potassium chloride cuprous oxide is formed and oxygen evolved. This is best demonstrated by adding cupric oxide in small quantities to a mixture of potassium and sodium chlorides a t 1000" and continuing the heating for one and a half hours. At the same time a basic cupric chloride is formed which by prolonged heating with sodium or potassium chloride solution is obtained as the compound 3Cu0,CuC12,4H,0. Phenomena of Diffusion in Metals in the Solid State and Cementation of Non-ferrous Metals.I. Cementation of Copper by means of Ferro-manganese. G. SIROVICH and A. CARTOCETI (Gaxxetta 1921 51 ii 245-261).-A bar of copper was arranged centrally in a porcelain tube glazed internally and the tube then packed with ferro-manganese containing 5% of wood charcoal both these materials being capable of passing through a sieve with 64 meshes per sq. em. and of being retained by one of 324 meshes per sq. em. The tube was closed by mcaiis of rubber stoppers luted with sodium silicate one of the stoppers having two holes to admit a thermo-couple for measuring the temperature and a glass tube bent a t right angles and with its end dipping into mercury. After the tube had been heated for some hours a t 900" in a Heraeus furnace considerable proportions of the manganese were found to have penetrated the copper (cf.J . SOC. Chem. Ind. 1922 1 7 ~ ) . T. H. P. E. H. R. Tervalent Copper. G. SCAGLIARINI and G. TORELLI (Gmzetta 1921 51 ii 225-228).-Contrary to Moser's statement (A. 1907 ii 549) the action of potassium persulphate on cupric hydroxide in presence of barium hydroxide a t temperatures obtained by cooling with ice and salt results in various changes in the colour of the solution and in the deposition of a tenuous amaranth-red precipitate which may be purified by repeated washing with ice- water by decantation. The compound thus obtained yields oxygen when treated with sulphuric acid oxidises hydrochloric acid with liberation of chlorine oxidises ammonia in the cold with production of nitrogen nitrous acid and traces of nitric acid decolorises per- manganate and decomposes potassium iodide with liberation of iodine in quantity greater than that corresponding with the pro- portion of copper present.Since i t does not yield hydrogen peroxide when treated with dilute acid the compound lacks the grouping characteristic of peroxides and is thus different from the orange- yellow copper peroxide obtained by means of hydrogen peroxide. The ratio between the percentages of copper and active oxygen present is in agreement with the formula Cu,03. T. H. P.INORGANIC CHEMISTRY. ii. 69 Production of Single Crystals of Aluminium and their Ten- sile Properties. H. C . H. CARPENTER and CONSTANCE F. ELAM (Proc. Roy. Soc. 1921 [A] 100 329-353; cf. A. 1921 ii 641).- A continuation of work previously published (Eoc.cit.) on the production of large crystals of aluminium. The metal used in the present work had a purity of 99.6y0 the impurity being 0.19% silicon and 0.14y0 iron. The test-pieces used were 70 mm. with a parallel portion 103 mm. long 26 mm. broad and 3 mm. thick and were estimated to contain 1,687,000 small crystals in the parallel portion (103 x 26 x 3 mm.). The authors first describe the treatment necessary to convert the whole of the crystals into a single crystal. Three separate processes are shown to be necessary (i) the aluminium strip is heated at 550" for six hours (ii) the strip after cooling is subjected to a stress which is equivalent to 378 kilos. per sq. cm. and gives an average elongation of 1.6% on 76 mm.(iii) the test- piece is finally placed in a furnace a t 450" and the temperature raised 15-20' per day up to 550' and then for 1 hour a t 600". Applying this treatment to thirty-eight test pieces showed that nine pieces consisted of a single crystal fourteen of two crystals nine of three crystals four of four crystals and two of six crystals. The tensile strength of aluminium strips consisting of known num- bers of crystals has been determined. It is shown that for strips consisting of 150 crystals per 25 mm. it is 708-740 kilos. per sq. cm. and these give an elongation of 36-38% on 76 mm. The tensile strength of strips consisting of a single crystal varies between 598 and 642 kilos. per sq. cm. and these strips suffer an elongation of 34-86% on 76 mm.The varying tensile strength and elongation was accompanied by differences in the type of stretching and fracture. Strips consist,ing of two crystals have a tensile strength of 441-550 kilos. per sq. cm. and suffer an elongation of 29-70y0 on 76 mrn. whilst strips consisting of three crystals have a tensile st'rength of 456-567 kilos. per sq. cm. and suffer an elongation of 36-55y0 on 76 mm. A further series of experiments on the pro- duction of single crystals in bars is described. The Thermal Treatment of certain Complex Aluminium Alloys. LBON GUILLET (Compt. rend. 1921 173 979-982).- In order to determine the effect of each constituent on the behaviour of duralumin under thermal treatment (cf. ibid. 1919 169 508) the author has studied alloys of aluminium and copper aluminium and silicon aluminium silicon and copper aluminium magnesium and silicon and quaternary alloys containing all four elements.Measurements of hardness have been made on annealed samples and on samples tempered a t different temperatures the measure- ments being made in the latter case immediately after tempering and also after the alloy had been kept for forty-eight hours a t 20". Prom the resulfs of these measurements and from micrographic examinations of the alloys it is shown that the simultaneous presence of silicon magnesium and copper is indispensable to obtain the interesting results given by tempering high resistance aluminium alloys. W. G. J. F. S.ii. 70 ABSTRACTS OF CHEMICAL PAPERS. Solubility Limits of Carbon in Ternary Steels.I. The System Chromiun-Iron-Carbon. KARL DAEVES (2. anorg. Chem. 1921 118 55-66).-Experiments were made to determine the influence of chromium on the solubility of carbon in iron and to determine the position of the corresponding solubility line in the ternary chromium-iron-carbon diagram. The solubility falls off rapidly at first as the chromium content increases then more slowly the general form of the curve being hyperbolic. Points on the curve were determined by observing what chromium content was necessary with a given carbon content to cause the appear- ance of a eutectic in the structure of the metal. To make the hard alloys workable for the preparation of polished surfaces it was necessary to heat for several hours a t SOO" just below the Ac point by which treatment the solid solution was broken up and the metal softened.Etching was accomplished by electrolysis in ammonium persulphate solution. In eutectoid alloys the cementite is practically unattacked by hot sodium picrate solution. Cold alkaline potassium ferricyanide turns the hard constituent of the eutectic brown to yellow leaving the mixed crystals untouched. The solubility curve explains many of the known .properties of chromium steels. The melting point of steel and the arrest points are little affected by chromium up to lo?&. [Cf. J . SOC. Chern. Ind. 1922 1 6 ~ . ] Solubility Limits of Carbon in Ternary Steels. 11. The System Tungsten-Iron-Carbon. KARL DAEVES (2. anorg. Chem. 1921 118 67-74).-The effect of tungsten on the solu- bility of carbon in iron was studied in the same way as that of chromium (preceding abstract) and a solubility curve of similar form was obtained separating eutectic from non-eutectic steels in the ternary diagram.Sudden changes in the physical properties of tungsten steels are correlated with changes of composition involving the passage from one side to the other of this limiting curve. The appearance of so-called double carbides of iron and chromium or of iron and tungsten observed by different workers is attributed to the same cause Small amounts of tungsten in E. H. R. steel raise the melting point but larger amounts depress it E. H. R. The Colour of Iron Alum. JANE BONNELL and EDGAR PHILIP PERMAN (T. 1921 119 1994-1997). Complex Selenates. JULIUS MEYER (2. anorg. Chem. 1921 118 147).-A large number of new complex selenates and incidentally some simpler compounds which have not hitherto been described were prepared for comparison with the corre- sponding sulphates.The new selenates described belong to the chromi- and cobalti-series and show the closest resemblance to the sulphates differing from these occasionally only in their water of crystallisation. On account of the ease with which selenic acid is reduced difficulties were a t times encountered in the preparation of certain of the compounds.lTORGANIC CHEMISTRY. ii. 71 [With LEONHARD S~~~c~.]-Chromiselenates. Violet chromic selenate [Cr(H20),],(Se0,),,3(or 4)H,O forms a crystalline powder readily soluble in water from which it is precipitated by alcohol or acetic acid.Its aqueous solution dissolves chromic hydroxide with formation of green basic salts. When the violet salt is heated in solution or in the solid state a t 90" it changes irreversibly into a green chromiselenate. The green salt prepared in the solid state has the composition Cr,(SeO,) 10H,O and dissolves very slowly in water probably only after addition of water. The green salt may have a constitution of the type [Cr(SeO,)(H,O),],SeO,. When a solution of the violet salt is boiled for some time a green compound is formed which is precipitated by alcohol as a green oil and dries to an amorphous green solid. It is very soluble in water and gives no precipitate with barium salts or with ammonia. It is probably a triselenatochromic acid [Cr( SeO,),]H,. ChloropentaquochromiseZenate [CrC1(H20),]Se0,,3H,0 was pre- pared from chloropentaquochromichloride and sodium selenate ; it forms a bright green powder very soluble in water and alcohol. Attempts to obtain other chloro-selenates corresponding with known chloro-sulphates were not successful.forms a green crystalline powder readdy soluble in water slightly so in alcohol. An attempt to prepare a corresponding double chromi-aluminium selenate failed although sulphates of the type [~C1,(H,o),](so,),[M(H2~)6] where M=Cr Fe Al or V were prepared by Werner and Huber (A. 1906 ii 170). Hexamminechromiselenate [Cr(NH,),],(seO,) was prepared from the corresponding nitrate and selenic acid. It is precipitated from aqueous solution by alcohol as a heavy yellow finely crystalline powder. The salt is amorphous whilst the corresponding sulphate has 5H20.Chloropentamminechromiselenate [CrCl(NH,),]SeO mas pre- pared from purpureochromichloride and silver selenate. It forms a heavy red amorphous powder sparingly soluble in water. The corresponding sulphate is much more soluble and crystallises with 2H,O. HexacarbamidechromiseZenate [Cr(NH2*CO*NH,)6]2( SeO,) pre- pared from hexacarbamidechromichloride and silver selenate was obtained as a bright green finely crystalline powder moderately soluble in water from which alcohol precipitates it. Triethylenediaminechromiselenate [Cr en,],(SeO,) from the corre- sponding chloride and silver selenate is a reddish-yellow heavy crystalline powder soluble in water and precipitated by alcohol. When the dry salt is heated a t loo" the colour changes to reddish- violet.Aluminium selemte which has not before been described forms a white crystalline powder easily soluble in water and precipitated by alcohol. It appears to contain less than 18H,O but the analysis did not distinguish between 15 and 17H,O. [With HANIT$ MOLRENHAUER.]-Comp~ex cobaltiselenates. The Dichlorotetraquochromihexaquochromiselenute [c~c~2(fI,o),l(seo,),~~~~~2o),l,ii. 72 ABSTRACTS OF CHEMICAL PAPERS. complex cobaltiselenates prepared were confined to those containing only one cobalt complex and to those with 6 5 or 4 molecules of ammonia or 4 molecules of pyridine. Hexammine ( lut eo) co balt isel enat e [ Co (NH ) ( S e 0,) 5H2 0 c orre - sponds in every respect with luteocobaltisulphate. Aquopentamminecobaltiselenate [CO.(H,Q)(NH,),]~(S~O,)~,~H~O was prepared both from the corresponding cobaltichloride and from selenatopentamminecobaltiselenate.The salt is similar in physical and chemical properties to roseocobaltisulphate. Diaquotetramminecobaltiselenate [ C!( H20)2(NI~3)4]2( Se04),,3H20 was prepared from carbonatotetramminecobaltiselenate and selenic acid. It dissolves in water to a deep red solution from which alcohol precipitates it as a bright red crystalline powder. It loses its water of crystallisation on exposure to air. Chloropentamminecobaltiselenate [CoC1(NH3),]SeQ4 was prepared from purpureocobaltichloride and silver selenate ; it corresponds in its properties with purpureocobaltisulphate. Chloroaquotetramminecobaltichloride selenate {[CoC1(H20) (NH3)41C112Se04 was obtained when dichlorotetrammincobaltichloride was treated with silver selenate through hydration of one of the nuclear chlorine atoms.It forms a violet crystalline powder giving a violet aqueous solution. Nitropentamminecobaltiselenate [ Co (NO,) (NH,) ,]SeO from the corresponding chloride and silver selenate forms bright yellow microscopic crystals giving a yellowish-brown aqueous solution. It forms a periodide as does the corresponding sulphate. [ Co (SO,) ( NH3),I,Se04,2H,0 was prepared from the corresponding sulphato- bromide and silver selenate. It is precipitated from aqueous solution by alcohol in rose-coloured leaflets consisting of microscopic rhombic tablets. The corresponding sulphatosulphate contains only 1H,O. Sulphatopentammineco baltiselenate Acid selenatopentamminecobaltiselenate [ co( SeO4)(NH3) 5]SeO4H,2H& was prepared by treating chloropeiitamminecobaltichloride with concentrated selenic acid.From the diluted solution the acid salt crystallised in reddish-violet crystal aggregates. It closely resembles the sulphato-sulphate and forms the starting material for the preparation of a series of selenatopentamminecobalti-salts including several of the following. [co(seo4> (NH3) 512(Se04) ,H20 was obtained by treating the above acid selenate with alcohol; it has a brighter red colour than the acid salt. SelenatopentarnminecobaltisuErphate [Co(SeO,) (NH3),],SO4,H2O was obtained from the selenato-bromide and silver selenate. It is precipitated by alcohol from aqueous solution in bright red lustrous tablets.This salt is metameric with the above sulphatopent- amminecobaltiselenate but the two are not isomorphous as the latter crystallises with 2H20. Xelenafopentamminecobaltinitrate [CO(S~O,)(NH,)~]NO~ was pre- Normal sel enat opent ammineco ba 1 t iselenat e ,I N ORGANIC CHEMISTRY. ii. 73 pared from the above acid selenate and ammonium nitrate. It separates in well-formed bright red sparingly soluble crystals. Selenatopentamminecobaltibromide [ Co( SeO,) (NH,),]Br was pre- pared from the above acid selenate and hydrobromic acid. It is thrown down by alcohol from aqueous solution as a bluish-red precipitate. Sel enatopentamminecobaltihexachloroplatinate [ Co ( S e 0,) (NH,) ,I2PfC1 2 H2 0 forms lustrous orange-red tablets sparingly soluble in water.In the tetramminecobalti-series only carbonic acid of the bi- valent acids could be introduced into the complex. With two univalent acid radicles stereoisomerism becomes possible and ,it was found possible t o prepare the 1 2- and 1 6-dinitrotetrammine- co baltiselenates. Carbonatotetramrninecobaltiselenates [ Co( CO,) ( NH,),],Se0,,3H20 is similar to the corresponding sulphate crystallising in dark red leaflets which lose their water of crystallisation on exposure to air. Acid dichlorotetramminewbaltiselenute [CoC12(NH,),]Se04H crys- tallises in dark green well-formed needles but is unstable and readily changes to the chloroaquotetrammine salt described above. Acid dichlorotetrapyridinecobaltiselenute [CoC1,Py4]Se0,H,2Hz0 is more stable than the dichlorotetrammine salt ; it crystallises in lustrous green leaflets. The salt corresponds with the sulphate described by Werner and Feenstra (A. 1906 i 450).1 2-Dinitrotetramminecobaltiselenute [ Co( N02)2(NH,),],Se0 was prepared from ffavocobaltinitrate (Jorgensen A. 1898 ii 592) and ammonium selenate; it forms dark brown crystah. 1 6-Dinitrotetramminecobalti~ele~te stereoisomeric with the last was prepared from croceocobaltichloride (Jorgensen Zoc. cit.) and silver selenate; it is precipitated from aqueous solution by alcohol in the form of minute bright yellow crystals. The electrical conductivities of many of the above salts in aqueous solution were measured a t 25" and their magnitudes were found to agree with the constitutions ascribed to the different salts.E. H. R. The Green Colour of Tungsten Trioxide. J. A. M. VAN LIEMPT (2. anorg. Chem. 1921 119 310-312).-Tungsten trioxide generally has a yellow colour but is sometimes green. A number of explanations of this phenomenon have been offered but it is now shown experimentally that the green colour is due to re- duction at ordinary temperatures by traces of organic matter to lower oxides. Provided the green oxide has not been ignited the yellow colour may be restored by heating it in a current of oxygen. E. H. R. Chlorination by Mixed Carbon Monoxide and Chlorine. F. P. VENABLE and D. H. JACKSON ( J . Elisha Mitchell Sci. Soc. 1920 35 87-89) .-Chlorination is successfully accomplished with a mixture of carbon monoxide and chlorine containing the former in excess in the following cases zirconium dioxide a t 480" stannic 3"ii.74 ABSTRACTS OF CHEMICAL PAPERS. oxide a t 400" magnesium oxide at 475" aluminium oxide a t 45OU ferric oxide a t 460" chromic oxide a t 625" manganese dioxide at 460" uranoso-uranic oxide at 500". With chlorine in excess the requisite temperature for zirconium dioxide is 425" and for ferric oxide 370". CHEMICAL ABSTRACTS. Antimonic Acid and the Use of Sodium Antirnonate in Analysis. E S . TOMULA (2. anorg. Chem. 1921 118 81- 92).-The constitution of antimonic acid and of the salts derived from it has never been satisfactorily settled and an attempt has now been made to solve the problem by the application of physico- chemical methods. The conductivity of the potassium salt was measured a t 25" a t dilutions from V=32 to 1024 and the basicity of the acid by the Oswald-Walclen rule was found to be 1.This rules out the possibility that the salt is a pyroantimonate K2H2Sb20 and since it gives a solution having an acid reaction it cannot be the metantimonate KSbO,. It must therefore be the orthoantimonate KH,SbO,. Hydrogen-ion determinations in a 1 /1024N-solution by the calorimetric method confirmed this view. The dissociation constant a t this dilution was found to be c(=0*957 and the hydrogen-ion concentration CH= 10-6'3. The equivalent conductivity of the sodium salt was on account of its low solu- bility determined only at dilutions V=512 and 1024 and was found to be of the same order as although slightly lower than that of the potassium salt. The hydrogen-ion concentration at V= 1024 was CH=10-6'4 and it is concluded that the two salts have the same constitution.Delacroix ( A . 1898 ii 340; 1900 ii 145) and Senderens (A. 1899 ii 557) both isolated a soluble and an insoluble form of antimonic acid which they called ortho- and pyro-acids but they differed as to which was which. Conductivity experi- ments on the potassium salts show that the soluble acid is the ortho-acid whether prepared by Senderens's or Dclacroix's method. It is concluded however that a concentrated solution of antimonic acid is not a true solution but a supersaturated colloidal pseudo- solution from which the acid soon separates in the insoluble form. Determinations were made a t 18" 25" and 33.5" of the solu- bility of sodium antimonate in water in aqueous sodium acetate and in aqueous methyl and ethyl alcohols.Expressed in mg. of Na,O,Sb,O,,GH,O per 100 C.C. of solution the solubility at 18" is in water 56.4 in equal volumes of water and ethyl alcohol 0.1 and in 2.5y0 sodium acetate 3.1. The following method is recommended for the estimation of antimony as sodium antimonate. The antimony must be in alkaline solution as sodium sulphantimonate Na,SbS4 and must be free from potassium since in presence of potassium salts pre- cipitation is incomplete. The solution is warmed a t 80" and stirred while a solution of 30% hydrogen peroxide is run in drop by drop until vigorous evolution of oxygen commences and it is then boiled until all oxygen evolution ceases. The alkaline solution is neutralised with acetic acid until it is acid to phenolphthalein but still weakly alkaline to litmus.It is stirred a further quarterINORGANIC CHEMISTRY. ii. 75 of an hour and then one-half its volume of 96% alcohol is added after which stirring is continued for ten minutes. After twelve hours the crystalline sodium antimonate is filtered washed on the filter with a solution containing 3 grams of sodium acetate 3 grams of acetic acid and 400 C.C. of ethyl alcohol per litre and finally with 50% alcohol. The dried precipitate is separated from the filter-paper which is burnt separately is ignited for fifteen minutes in a porcelain crucible and weighed as sodium metanti- monate NaSbO,. Special directions are given for procedure when tin is present as it is then. necessary to redissolve and re- precipitate the sodium antimonate.[See also J . Xoc. Chem. Ind. 1922 12A.1 E. H. R. The Reaction Limit of Chemical Agents on Copper-Gold Alloys and their Galvanic Tension. G. TAMMA" (2. anorg. Chem. 1921 118 48-54).-The reaction limit in different copper-gold alloys is reached when the molecular fraction of gold present is 1/8 2j8 or 4/8 according to the chemical reagent used. The reactivity of the mixed crystals may be regarded as due to the loosening of the copper atoms from their lattice combination by the chemical agent or from another point of view to the action of the chemical agent on copper atoms which have become detached from the lattice on account of their solution tension. From the latter point of view it was important to determine how the solution tension of the alloys varied with the composition.Measurements were made against a gold electrode in a number of electrolytes and against silver with silver sulphate as electrolyte. The results showed that the limiting composition beyond which no copper ions appear in the solution and the alloy behaves electrically as pure gold is a t 2/8 mol. fraction of gold. This method does not give such sharp limiting values as the chemical method however owing to the sensitiveness of the galvanic tension to impurities on the surface of the metal. The case of the cell silver I saturated silver sulphate I copper-gold is specially interesting since when the proportion of gold in the alloy does not exceed 0.145 mol. silver is visiblyprecipi- fated and the metal becomes negatively charged whilst the alloys richer in gold do not precipitate silver and assume a weak positive charge. This weak positive charge indicates a superficial deposit of silver so that the surface acts as a silver-gold alloy of corre- sponding composition. It is shown from consideration of the mixed crystal lattice that when 1/8 mol. of gold or less is present in the copper alloy conditions are favourable for the formation of silver crystals. It is suggested that those agents which find their active limit a t 2/8 mol. of gold corresponding with the solution tension limit for copper ions act first on the copper ions in solution but as soon as the osmotic pressure of the copper ions exceeds the solution tension the agent attacks the mixed crystal surface. E. H. R. Ruthenium Tetroxido. F. KRAUSS (2. anorg. Chem. 1921 119 217-220) .-An aqueous solution of ruthenium tetroxide has 3*-2ii. 76 ABSTRACTS OF CHEMICAL PAPERS. apparently a weak acid reaction although this is dificult to demon- strate on account of the rapid decomposition of dyes by the solution. The solution behaves as an electrolyte and is decomposed by the current with formation of a green colour. With alkali hydroxides it forms salts but only the ammonium salt could be obtained in the pure state. It was prepared by adding concentrated ammonia to a concentrated solution of ruthenium tetroxide in water until the colour changed from yellow to greyish-brown. By evaporating a salt of the composition (NH,),RuO was obtained. Under certain conditiona which could not be accurately determined a mono- and a di-hydrate of this salt were obtained. In the preparation of ruthenium tetroxide besides the yellow compound a brownish- red substance was observed less soluble in water than the tetroxide. This has not been identified. Ruthenium tetroxide can be estim- ated by distilling it in a current of dry air at 15" into a specially constructed weighed flask dissolving in a little water reducing with alcohol evaporating with dilute hydrochloric acid igniting in a stream of hydrogen and weighing the ruthenium. E. H. R.

ISSN:0368-1769    

DOI:10.1039/CA9222205044

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 76 ABSTRACTS OF CHEMICAL PAPERS. Mi n e r a1 ogi c a1 Chemistry . Native Antimony from Kern County California. C. H. BEHRE JUN. (Amer. J. Xci. 1921 [v] 2 330-333).-A statement of the results of an examination of nodular masses of antimony with a crust of oxidation products. L. J. S . Identity of Flagstaffite with Terpin Hydrate. F. N. GUILD (Arner. Min. 1921 6 133-135).-A comparison of the crystal constants of flagstaffite (A 1921 ii 51) with those of terpin hydrate suggests the identity of these ; and this is confirmed by comparative tests made on the natural and artificial materials. Variable results for the m. p. are obtained owing to loss of water before melting. When heated very slowly the crystals soften at about loo" and finally melt near 116". Anhydrous terpin from flagstaffite has m.p. 105". The terpin hydrate formula C1,H,,02,H,0 is adopted since the material analysed had been partly dehydrated by remaining over sulphuric acid. The Natural Iron Hydroxides. KARL WILLMANN (Centr. Min. 1921 673-678).-A review is given of the colloidal and crystalline forms of iron hydroxides. The scaly (Rubinglimmer) m d acicular (Samtblende or needle-iron-ore) forms of goethite differ in optical characters and are regarded as dimorphous forms of Fe,O,,H,O. New analyses of Rubinglimmer from the Eleonore mine near Giessen gave Fe,O 89-90 H,O 10*77=100-67 and Fe,O 88.11 H,O 11.97=100-08 agreeing with this formula. L. J. S. I;. J. S.ANALYTICAL CHEMISTRY. ii. 77 Curite a New Radioactive Mineral. ALFRED SCHOEP (Compt. rend. 1921 173 1186-1187).-The new mineral is found at Kasolo Katanga Belgian Congo as translucent reddish- brown acicular crystals on torbernite or as compact or earthy masses and consists of minute needles with straight optical extinction. It is readily soluble in cold nitric acid and in hot hydrochloric acid; when heated it turns dark brown. Analysis gives the formula Pb0,5U0,,4H20. PbO. uo,. H,O. Fe,O,. Total. d" 21-32 74.22 4.00 0.17 99.7 1 7.192 L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9222205076

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytieal Chemistry. ii. 77 The Conditions for the Maximum Precipitation of an Amphoteric Electrolyte. ADA PRINS (Chem WeekbZad 1921 18 657-658).-The minimum solubility occurs a t a definite hydroxyl-ion concentration depending for each amphoteric electro- lyte on its solubility product as base and as acid. The concentrations of the positive and negative ions are inversely proportional to their charges. s. I. L. Use of Caesium Chloride in Microchemistry. ENRIQUE HERRERO DUCLOUX (Anal. Asoc. Quim. Argentina 1921 9 215- 227).-Caesium chloride may be used as a reagent in micro- chemistry by reason of the well-defined double chlorides which it forms with different metals. Crystallographic descriptions with photomicrographs are given of the double salts thus formed with silver mercury lead platinum gold palladium arsenic antimony cadmium tin copper aluminium iron zinc nickel cobalt man- ganese calcium magnesium thallium cerium and indium.G. W. R. Use of the Zeiss Water Interferometer (Rayleigh-Lowe) for the Analysis of Non-aqueous Solutions. ERNST COHEN and H. R. BRUINS (Proc. K. Akad. Wetemch. Amsterdam 1921 24 114-122).-A description of the Rayleigh-Lowe water inter- ferometer and the method of use for estimating the concentration of aqueous solutions are given. The accuracy obtainable with this instrument is about 99.9998% for aqueous solutions. To use this instrument for non-aqueous solutions greater precautions in the fixing of the temperature are required. The thermostat liquid should also be chosen so as to have a refractive index of the same order as that of the solvent used.When these precautions are taken an accuracy equal to that obtained for water solutims may be obtained with solutions in organic solvents. J. F. S,ii. 78 ABSTRACTS OF CHEMICAL PAPERS. A Buffer Solution €or Colorimetric Comparison. T. C. MCILVAINE ( J . BioZ. Chem. 1921 49 183-186).-The author covers the whole range from PII 2.2 to PH 8.0 by mixing two solu- tions only viz. a O.2M-disodium phosphate solution with 0-1M-citric acid. A table to obtain any desired PH is given and also a graph. G. B. A Simplified Form of Apparatus for Air Analysis. CHARLES CLAUDE GUTHRIE (J. BioZ. Chem. 1921 48 365-371).-The apparatus which is illustrated in the original “ differs from the well known forms in dimensions rather than in principles or in design.” E.S. Estimation of the Gases of the Blood. DONALD D. VAN SLYKE and WILLIAM C. STADIE ( J . BioZ. Chem. 1921 49 1-42).- Improvements in the technique of using the apparatus previously described for the extraction from the blood and measuring of the carbon dioxide (A. 1917 ii 422423) oxygen (A. 1918 ii 82) and carbon monoxide (A.? 1920 ii 53). All the gases can now be estimated in 1 C.C. of blood by a modified form of the original apparatus with narrow measuring tube enclosed in a water-jacket. In the oxygen estimation the blood is now laked with water and the amount of ferricyanide has been greatly reduced; the results are about 5% higher than those obtained by Haldane’s method. Particularly in the case of the carbon dioxide estimation the errors are fully analysed and examples of calculations are given. G.B Mechanical Shaker and other Devices €or Use with the Van Slyke Blood Gas Apparatus. WILLIAM C. STADIE (J. Bid. Chem 1921 49 43-46 ; cf. preceding abstract).-A motor- driven shaker a levelling scale and tonometer rotator are de- scribed with the help of figures. SCHIMMEL & Co. (Bey. Xchimmel & Co. 1921 56-61; from Chem. Zentr. 1921 iv 771).-Benzaldehyde is burnt in a small lamp so constructed that the amount of liquid burnt may be found by weighing a t the beginning and end of the experiment. The products of com- bustion are passed through two U-tubes containing glass beads moistened with O-OBN-potassium hydroxide solution foaming being prevented by the use of a few drops of petroleum. The washings from the absorption apparatus are united and after addition of an equivalent amount of O-OQN-sulphuric acid con- centrated in a closed flask.The solution is then made alkaline to phenolphthalein and the colour discharged by one or two drops of 0-02N-sulphuric acid. Five drops of 10% potassium chromate solution are added and the chlorine is estimated in the usual way with 0-02N-silver nitrate solution. Action of Potassium Ferrocyanide on Silver Haloids. G. B. BONINO (Gaxzetta 1921 51 ii 261-265).-Potassium ferro- cyanide does not appear to interact with silver bromide or iodide G. B. Estimation of Chlorine in Benzaldehyde. G. W. R.ANAL'YTICAt CHEMISTRY. ii. 79 buti with the chloride it reacts according to the equation 3AgC1+ K,Pe(CN),=Ag,KFe(CN) ,+3KC1.The chlorine ion may there fore be estimated in presence of the iodine ion by precipitating and washing the mixed silver haloids treating the latter with a known volume of 0.W-potassium ferrocyanide solution removing the insoluble silver potassium ferrocyanide by filtration and determining the amount of the residual potassium ferrocyanide by titration with standard permanganate solution. The reaction has not yet been studied quantitatively in presence of bromides. T. H. P. Estimation of Small Quantities of Bromides and Chlorides in Iodides. I. M. KOLTHOFF (Pharm. Weekblad 1921 58 1568-1569).-The iodide in solution is treated with excess of sodium nitrite in presence of sulphuric acid. After filtering and boiling to remove iodine and excess of nitrous acid chlorides and bromides are estimated by Volhard's method.The method is quantitative but does not distinguish between chlorides and bromides. s. I. L. Bromine Normally Present in Animal Tissues. A. DAMIENS (Bull. Sci. Pharmacol. 1921 28 85-93; from Chem. Zentr. 192 1 iv 847) .-Thirty grams of finely-divided tissue are extracted by heating with dilute potassium hydroxide solution. The dried residue is incinerated with a mixture of potassium nitrate and sodium carbonate and the ash dissolved in water. Iodine is estimated in a portion of the solution as follows the silver haloid precipitate obtained by addit'ion of silver nitrate solution in the presence of nitric acid is suspended in water and a stream of chlorine is passed first in the cold and then in the presence of 1 C.C. of sulphuric acid with warming.Air is passed through and the precipitate removed by centrifuging. The iodine is then estimated by a colorimetric method. Another portion of the solution is precipitated with silver nitrate and nitric acid. The precipitate is removed and the filtrate is treated with zinc and sulphuric acid. When less than a milligram of iodine is present bromine may be estimated colorirnetrically in the filtrate. In the presence of larger amounts of iodine the filtrate after the reduction of the silver haloid precipitate is neutralised with ammonia diluted to 40 C.C. and after addition of 1 gram of iron animonium sulphate concentrated to 10 C.C. Bromine may then be estimated as before (cf. A. 1921 i 476).Estimation of Sulphur in Pyrites. L. GADAIS ( A m . Chim. Analyt. 1921 3 330-335).-A critical review of Lunge's method and certain suggested modifications. For accurate work the original method without alteration is to be preferred care being taken to adhere strictly to all details of the operations. A varia- tion of this method in which the insoluble gangue is not filtered off before the precipitation of the iron with ammonia is not recom- mended as this gangue contains substances such as the sulphates of barium strontium calcium and lead which may be partly G. W. R.ii. 80 ABSTRACTS OF CREMICAL PAPERS. dissolved by ammonia and reprecipitated on subsequent acidifica- tion and addition of barium chloride. A second modification of Lunge’s procedure which obviates the washing of the gangue consists in making up the solution in aqua regia to 100 c.c.filtering off 50 c.c. and proceeding with this aliquot portion as in the original method. This is free from serious objection provided the insoluble residue is comparatively small in amount. Finally a rapid control method not suitable for accurate work consists in diluting the original solution to about 800 c.c. adding ammonia directly to this digesting for two hours a t a moderate temperature cooling making up the volume to 1000 c.c. and filtering off 500 C.C. in which sulphate is estimated in the usual way. Volumetric Estimation of Sulphide by Oxidation to Sulphate. H. H. WILLARD and W. E. CAKE (J. Amer. Chem. XOC. 1921,43 1610-1614).-Sulphide is rapidly and quantitatively oxidised to sulphate by an excess of hypobromite in 26N-sodium hydroxide or by hypochlorite in 4N-sodium hydroxide.The excess of oxidising agent is determined iodometrically. The method gives accurate results for the estimation of sulphur in steels and in sulphides if care is taken to exclude all other reducing agents. I n the case of steels the method is used as follows 5 grams of steel are placed in a flask through which hydrogen may be passed which is connected with a 10-bulb tube for absorbing the hydrogen sulphide. Air is removed from the apparatus by hydro- gen and 100 C.C. of hydrochloric acid (d 1.1) are added. After the reaction has moderated the solution is heated just to boiling for five minutes after the steel has dissolved. The solution in the absorption tube should contain 6-7 grams of sodium hydroxide in 60 C.C. of solution.The contents of the bulbs are washed with as little water as possible into a flask containing 10 C.C. of 0-3h7- hypobromite solution and kept for three or four minutes then 2 or 3 grams of potassium iodide are added and the solution is diluted to 150 C.C. It is then exactly neutralised with concentrated hydrochloric acid and 5 C.C. excess added and titrated with 0.1N- sodium thiosulphate. If hypochlorite has been used instead of hypobromite more sodium hydroxide must be used. Sulphides which are soluble in hydrochloric acid are estimated in the same way as steels. Insoluble sulphides are ignited with powdered iron in an atmosphere of hydrogen or carbon dioxide thus producing ferrous sulphide.The estimation is then carried to completion as above. Estimation of Sulphurous Acid. VICTOR COPPETTI (Ann. Chim. Analyt. 1921 3 327-330).-The gravimetric method of Haas for the estimation of sulphurous acid which consists in expelling the sulphur dioxide from the solution under examination by distillation in an atmosphere of carbon dioxide absorbing the gm in a solution of iodine and weighing the resulting sulphuric acid as barium sulphate gives accurate results volumetrically if means are taken to prevent loss of iodine by volatilisation in the G. P. M. The error of the method is about 0.1%. J. F. S.ANALYTICAL CHEMISTRY. .ii. 81 current of carbon dioxide. For this purpose an apparatus is described consisting essentially of a 300 C.C. flask to contain the iodine solution to the bottom of which extends the gas delivery tube from the distillation flask.Surmounting the flask is a spherical absorption vessel containing N/10-thiosulphate solution through which the carbon dioxide and iodine vapours leaving the flask must pass. When distillation is complete the thiosulphate solution containing all the volatilised iodine is allowed to run back into the flask and the excess of iodine in the latter is titrated back with standard thiosulphate solution. The Estimation of Sulphates by means of a Suspension of Barium Chromate. I. M. KOLTHOFF (Rec. trav. chirn. 1921 40 686-699; cf. Andrews A. 1890 414).-Although it would appear on theoretical grounds that an estimation of sulphate by means of barium chromate was not practicable the method is valid since the reaction BaSO,+CrOi’ zz BaCrO,tSO,” proceeds very slowly from left to right.The solution acidified with hydrochloric acid should be heated during neutralisation with ammonia to avoid the loss of chromic acid which accompanies the precipitation of barium chromate at ordinary temperatures and having regard t o the hydrolysis of ammonium chromate a slight excess of ammonia should be added. Barium chromate is adsorbed by ferric aluminium and zinc hydroxides so that when these metals are present the method gives results which are too low but trustworthy results can be obtained when ions which affect the reacting substances are absent. I n presence of calcium the results are too low the error becoming smaller with increasing acidity of the solution and decreasing concentration of calcium.Practical details are given. G . F. M. H. J. E. Catalytic Action of Copper in the Oxidation of Ammonia by means of Persulphate. G. SCAGLIARINI and G. TORELLI (G‘axxetta 1921 51 ii 277-280).-Quantitative investigation of the oxidation of ammonia by means of either potassium or ammo- nium persulphate in presence of copper sulphate shows that the oxygen of the persulphate first oxidises the ammonia to nitrous acid which is converted into ammonium nitrite this being decom- posed with liberation of nitrogen by the heat developed 2NH3+ 30,=2HN02+2H20 2NH3+2HN0,=2NH4*N02 and 2NH4*N02 =4H20+2N,. The catalytic effect of copper salts appears to be due to oxidation of the copper to a more highly oxidised com- pound which passes on its surplus oxygen to the ammonia.The estimation of persulphate by means of ferrous salts may be replaced advantageously by the following method in which use is made of a Schultze and Tiemann’s apparatus furnished with a mercury valve (2. anal. Chem. 1870 9 401; Ber. 1873 6 1041) 40 C.C. of water and 0.4-0.6 gram of copper sulphate are boiled in the flask for about ten minutes the caoutchouc tube being then clipped and the boiling continued for five minutes to expel the air. The apparatus is allowed to cool the mercury rising inii. 82 ABSTRACTS OF CHEMICAL PAPERS. the barometer tube and a vacuum becoming established in the flask. A known volume of the persulphate solution and after- wards about 100 C.C. of ammonia solution are drawn into the cold flask through the clipped tube the flask being then heated and the evolved gas collected over water and measured.The results obtained in this way agree exactly with those yielded by the ferrous sulphate method. [Method for the Estimation of Tri- Tetra- and Penta- thionates present together in Solution with Sulphite Thio- sulphate and Sulphate.] E. H. RIESENFELD and G . W. Fmn (Z. anorg. Chem. 119 225-270). The Accuracy of Dumas's Method for the Estimation of Nitrogen in the Cases of Substances rich in Nitrogen. ERNST Mom (Ber. 1921 54 [B] 2758-2767).-A mathematical treat- ment of the influence of the errors in measuring weight of substance volume of nitrogen temperature and pressure on the accuracy of the process. The usual procedure of estimating the volume accurately tlo within 0.05 or 0.1 c.c.and the temperature and pressure to degrees Centigrade and millimetres of mercury is sufficient for substances containing 20-25 yo of nitrogen but involves considerable error when more than this amount is present. The errors due to inaccurate reading of pressure and temperature cannot be minimised by increasing the weight of substance taken. On the other hand the errors due to volume and weight of substance become con- siderable when a small quantity of substance is taken and can be diminished by increasing the amount. The practice of using small weights of material when dealing with substances rich in nitrogen by Dumas's method is to be deprecated; Pregl's method should be used in preference. The error involved in the measurement of pressure does not depend to an appreciable extent on whether the gas is moist or dry (above 50% potassium hydroxide solution) but the error involved in measurement of temperature is lower in the latter case.In spite of this fact the measurement is generally made in preference over water by reason of the customary large diameter of the Schiff's nitrometer and the formation of foam over the potassium hydroxide solution. The temperature is first brought to whole degrees by addition or subtraction of x" in the direction of smallest change and the pressure is then changed by 3x mm. in the same sense as the alteration of temperature. A plea is entered for the more uniform recording of analytical data in the literature and more precise statement of the exact condition of the nitrogen with respect to moisture as also for the reduction of pressures to 0".The Kjeldahl Nitrogen Method and its Modifications. A. E. PAUL and E. H. BERRY ( J . Assoc. O#. Agric. Chem. 1921 5 108-1 32) .-Investigations are described into the most suitable T. H. P. See this vol. ii 45. A simple and accurate method of calculation is as follows. H. W.ANALYTICAL UHEMISTRY. ii. 83 apparatus and method for the nitrogen estimation with particular reference to the case of cotton-seed meal as presenting special difficulty. The most suitable type of bulb-trap for use in the distillation is the one in which both inlet and outlet tubes enter the bulb and are bent in opposite directions. It is advisable although not absolutely necessary to have enough acid in the receiver to neutralise all the ammonia distilled.Practically all the ammonia appears in the first 75 C.C. of the distillate and all is in the first 100 C.C. During the initial digestion of the material with acid the flame should never touch the flask above the surface of the liquid; the flask should be protected by a ring of asbestos. The volume of the digesting liquid should a t no time be less than 10 C.C. If mercury is used to aid the digestion there is a loss of from 2 to 15% of ammonia unless enough potassium sulphide is added to precipitate all the mercury before distillation. The use of copper sulphate during digestion does not necessitate the sub- sequent addition of potassium sulphide. The use of perman- ganate is unnecessary.Digestion with sulphuric acid alone never gives maximum results. Mercury gives a much more rapid digestion than copper salts and potassium sulphate is more efficient than sodium sulphate. The most rapid and efficient digestion is given by the use of 0.7 gram of mercuric oxide and 10 grams of potassium sulphate. In this way the liquid becomes clear in one to one and a half hours and further heating for three hours completes the digestion. The amount of copper used in the digestion has little effect on the result. A 2 gram sample of cotton-seed meal and similar substances is preferable. Digestion should not be carried out in an atmosphere containing nitrous fumes. Nitrates in the digestion mixture are not only entirely lost but they also bring about a considerable reduction in the amount of ammonia recovered.A. G. P. Modification in the Kossel-Neumann Method for the Estimation of Phosphorus in Organic Substances. MARIO A. MANCINI (Biochem. ter. sper. 1921 8 4-7; cf. Falk and Sugiura A 1915 ii 577).-@5 Gram of the substance is heated in a 200 C.C. Kjeldahl flask with 6-8 C.C. of sulphuric acid (d 1*184) the boiling being continued for one hour. Nitric acid (d 1.4) having been carefully added drop by drop boiling is con- tinued until the evolution of oxides of nitrogen ceases. The opera- tion is repeated four or five times. The clear light yellow liquid is washed into a beaker with hot water and ammonium hydroxide solution is added in slight excess followed by 30-40 C.C. of 40% ammonium nitrate solution and 20 C.C. of .%yo nitric acid.The liquid is mixed a t loo" with 120-140 C.C. of a boiling 3% solution of ammonium molybdate. After being kept for a t least two hours it is filtered and the precipitate washed with a hot solution containing 50 C.C. of nitric acid and 50 grams of ammonium nitrate per litre. Hot 25% ammonium hydroxide solution is poured over the filter which is washed with hot water until the washings give no reaction with Nessler's reagent. To the filtrate is addedii. 84 ABSTRACTS OF CHEMICAL PAPERS. 50 C.C. of ammoniacal " magnesia mixture," and after being kept for twenty-four hours the precipitate is filtered washed and ignited in the usual manner. The Composition and Preparation of a Neutral Solution of Ammonium Citrate. C. S. ROBINSON ( J . Assoc. Ofl.Agric. Chern. 1921 5 93-97).-To overcome the confusion attached to the term " neutral ammonium citrate solution," it is recom- mended that such a solution should be one showing a pH value of 7.0. The solution contains 45.33 grams of ammonia and 172.00 grams of anhydrous citric acid per litre a t 20" and has d 1.09. To prepare a litre of solution 172.00 grams of anhydrous citric acid are dissolved in 700 C.C. of water nearly neutralised cooled and made up to a convenient volume maintaining the density above 1.09. Of this 5 C.C. are diluted to about 20 c.c. and standard ammonia solution is added until the colour produced with phenol-red indicator matches that produced with the same quantity of indicator by an equal volume of neutral standard phosphate solution (50 C.C.of M/5-dihydrogen potassium phosphate +29*63 C.C. of M/5 sodium hydroxide in 200 c.c.). The calculated amount of ammonia is then added to the bulk of the solution. A. G. P. CHEMICAL ABSTRACTS. A Modified Method for the Estimation of Phosphoric Acid. A. W. CLARK and R. F. KEELER ( J . Assoc. 08. Aqric. Chern. 1921 5 103-105).-Two grams of the sample are dissolved in 30 C.C. of concentrated nitric acid and 10 C.C. of hydrochloric acid. The solution is diluted to 200 C.C. and filtered through a dry filter. A portion equivalent to about 0.25 gram is neutralised with ammonia and acidified with nitric acid. Fifty C.C. of 20% ammon- ium nitrate solution are added and then sufficient ammonium molybdate solution. After remaining over-night the precipitate is collected on a Gooch crucible washed eight times with 2% nitric acid (12-13 C.C.each time) then twice with cold water and dried for two hours a t 120". Precipitation in the cold and drying a t 120" give a less variable precipitate than the usual method. The conversion factor of ammonium phosphomolybdate to phosphoric acid is 0.03723. Nephelometric Method for the Estimation of Phosphoric Acid and its Compounds in Small Quantities of Blood. W. R. BLOOR (Bull. SOC. Chim. Biol. 1921 3 451475).-A detailed description of the author's adaptation (A. 1918 ii 452) of Kober and Egerer's method (A. 1915 ii 794). Toxicology of Arsenic. N. TARTJGI (Boll. Chim. Farm. 1921 60 569-576) .-The results of experiments with rabbits and guinea-pigs show that arsenic either organically combined or mixed mechanically with organic matter always yields gases containing arsenic when putrefaction occurs. Such evolution of gas may occur quickly and must be borne in mind in cases of suspected arsenical poisoning.In the putref action of animal matter the mechanism by which gaseous arsenic compounds are formed A. G. P. E. S.ANALYTICAL CHEMISTRY. ii. 85 is more complicated than the action of the " arsenic moulds," since such gases are not formed in the initial stages of the putre- faction where aerobiosis appears to predominate and since also the gases contain not only alkylarsines but hydrogen arsenide as well. T. H. P. f The Use of Silica Crucibles for the Estimation of Potassium in Soils. J. S. JONES and J. C. REEDER (Soi2 Sci. 1921 12 419-432).-For the estimation of potassium in soils by the fusion method silica crucibles may be used instead of platinum provided that certain limits of temperature are observed.To ensure perfect fusion the muffle must reach a temperature of 812" and to avoid loss of potassium by volatilisation the tem- perature must not exceed 855". For this purpose an electrically heated muffle is preferable. An electrical arrangement for heating a silica crucible of the J. L. Smith type 10 cm. long 2 cm. in diameter at the top and 1.8 cm. at the bottom is described and is very satisfactory for this type of work. Detection of Magnesium in Presence of Manganese and Phosphoric Acid. A. PURGOTTI (Guxxetta 1921 51 ii 265- 266).-In presence of phosphoric acid manganese is precipitated almost completely as tertiary manganous phosphate even from solutions containing large proportions of ammonium chloride ; the precipitate undergoes gradual or in the hot rapid trans- formation into pale pink crystals of manganous ammonium phosphate analogous in composition and properties to magnesium ammonium phosphate.The formation of this manganese pre- cipitate and hence the danger of mistaking it for the magnesium precipitate may be avoided by treating the hydrochloric acid solution not only with ammonia solution to remove the kations accompanying magnesium but also a t the same time with ammonium sulphide which eliminates the whole of the manganese as sulphide; the filtrate is then tested for magnesium. If the metals of the third group are precipitated in the usual way with ammonia solution manganese phosphate is precipitated in considerable quantity in addition to certain amounts of calcium barium and strontium phosphates a little manganese and much calcium barium and strontium passing into solution.Similar behaviour is shown by a mixture of magnesium phosphate with a manganese salt but less magnesium goes into solution and still less manganese is precipitated as phosphate. If the quantity of manganese salt is very considerably greater than that of the calcium barium and strontium phosphates the equilibrium Ca3(P0,)2+ 3Mn(OH) s lHn3(POp),+3Ca( OH) is displaced towards the right hand side and the calcium barium and strontium pass into solution almost completely. Apparatus for the Gasometric Estimation of Zinc in Zinc Powder.EDGAR BEYNE (Ann. Chim. Amlyt. 1921 3 360).- The apparatus consists of a gas burette the upper part of which below the glass stop-cock is expanded into a bulb of 300 C.C. W. G. T. H. P.ii. SG ABSTRACTS OF CHEMICAL PAPERS capacity and the lower part is graduated in 0.5 C.C. from 300 C.C. to 375 C.C. The lower end of the burette is connected with a rubber tube to a bulb for adjusting the liquid level and gas pressure in the burette and the upper end is connected through a small refrigerating spiral to a Koninck apparatus which is charged with the zinc dust under examination and a mineral acid. In a simpler form of apparatus the latter is replaced by an ordinary flask con- nected by means of a glass tube with the stop-cock of the burettc. G. F. M. The Direct Iodometric Estimation of Lead Peroxide.SAMUEL GLASSTONE (T. 1921,119 1997-2001). A Very Sensitive Reagent for Copper the Kastle-Meyer Reagent. PIERRE THOMAS and GEORGES CARPENTIER (Cmpt. rend. 1921 173 1082-1085).-The Iiastle-Meyer reagent which is a 2% solution of phenolphthalein in 20% potassium hydroxide solution decolorised by boiling with zinc powder gives a pink coloration with copper salts and is capable of detecting 1 part of copper in 100,000,000 parts of water. Four drops of the reagent are added to 10 C.C. of the solution to be tested and then one drop of hydrogen peroxide ( 5 - 4 vols.). The Iodometric Estimation of Copper and Arsenic present together especially in Paris and Schweinfiirth Green. I. M. KOLTHOFF and C. J. CREMER (Pharm. WeeEbZad 1921 58 1620-1624).-Arsenic trioxide can be estimated by means of iodine if the cupric-ion concentration is very much reduced which can be effected by addition of excess of pyrophosphate or tartrate with which the copper forms complex salts.O*& 0.8 Gram of the pigment is boiled with 25 C.C. of water and 5 grams of sodium pyrophosphate to LL clear solution. After cooling N/lO-iodine solution is added until the deep blue solution becomes green; the end-point is very sharp. The iodine required is equivalent to the arsenious oxide present. Ten C.C. of QN-sul- phuric acid and 2 grams of potassium iodide are then added and after ten minutes the iodine liberated by reduction of the cupric compound is titrated with N/lO-thiosulphate starch being added towards the end.The results were checked by analysis of the pigments by the standard Lunge-Berl method This method was found unsatis- factory for copper the results being always high. Addition of hydrazine sulphate before the sodium hydroxide reduces the copper compound the element being precipitated and weighed as metal ; this modification is much more accurate than the accepted method. The iodine titration is rapid and simple a'nd gives accurate results for both elements. Separation and Estimation of Copper Lead Antimony and Tin. Analysis of White Metals. A. &ING and A. LASSIEUR (Compt. rend. 1921 173 1081-1082).-05--1~0 Gram of the alloy is dissolved in 10 C.C. of hydrochloric acid in the presence of potassium chlorate. The solution is diluted to 100 c.c. W. G. s. I. L.ANALYTICAL CHEMISTRY.ii. 87 and neutralised with sodium hydroxide. Any precipitate formed is redissolved by the addition of 4 - 5 grams of tartaric acid. The liquid is transferred to a conical flask coated inside with wax and to it are added 10 C.C. of concentrated hydrofluoric acid and then after half an hour 10 grams of sodium acetate 1 C.C. of glacial acetic acid and water to bring the volume to 300 C . C . A white precipitate of lead fluoride is formed but to the liquid 20 C.C. of a 10% solution of sodium sulphide are added and after a time the precipitate of the sulphides of copper lead and antimony is filtered off. In the filtrate the tin may be estimated either by precipitation with cupferron (cf. A 1920 ii 452) or electrolytically after decomposition of the complex fluoro-compound by the addition of boric acid and redissolving the tin sulphide by boiling with hydrogen peroxide.The precipitate of the mixed sulphides is extracted with 80 C.C. of sodium sulphide solution (d 1.14) and the antimony estimated electrolytically in the extract after the addition of potassium cyanide. The copper and lead sulphides are dissolved in nitric acid and the two metals estimated simul- taneously by electrolysis. W. G. Estimation of Mercury in the Mercurial Pills of the [French] Codex. MAURICE FRANQOIS ( J . Pharm. Chim. 1921,24 369-379; Ann. Palsif. 1921 14 340-347).-The pills are heated with concentrated nitric acid for two hours on a water-bath and after a further two hours the solution is filtered and the destruction of the organic matter is completed by adding a small quantity of a 10% solution of bromine.After ten minutes the liquid is rendered strongly alkaline with sodium hydroxide and after adding potassium iodide the mercury is precipitated in the form of a grey powder by means of formaldehyde solution. After two hours the supernatant liquid is decanted through a filter the mercury is washed with dilute sodium hydroxide solution and is then treated together with the filter-paper and its contentp with diluted acetic acid and AV/lO-iocline solutiou. After ten minutes’ agitation the mercury is completely transformed into mercuric iodide which dis- solves in the potassium iodide present and the excess of iodine is titrated back with tlhiosulphate. The method is of general application to all the mercurial pills of the French Codex without modification except in the case of opiated mercurous iodide pills with which after treatment with nitric acid a crystalline precipitate of mercuric iodonitrate HgI,,Hg(NO,) is formed.All that is necessary in this case however is t o dissolve the crystals in the liquor by addition of potassium iodide and omitting the bromine treatment to proceed with the precipitation of the mercury as*above. In pills containing soap although the f a t acids are not destroyed by the nitric acid treatmen@ they do not retain any mercury in combination and form a layer on the surface of the liquor which solidifies on cooling and is therefore easily separated. ERNST JOSEF KRAUS (Chem. Zeit. 1921 45 1173).-The neutral or faintly acid solution containing the aluminium in the form of sulphate and free from G.F. M. Volumetric Estimation of Aluminium.ii. 88 ABSTRACTS OE' CHEMICAL PAPERS. other interfering metals is titrated with standard disodium hydro- gen phosphate solution a few drops of silver nitrate solution being used as indicator as yellow silver phosphate only commences to form after all the aluminium has been precipitated as phosphate according to the equation A12(S04),+2Na,HP04~2A1P0,+ 2Na,S0,+H2S0,. The titration is preferably carried out in a boiling solution as the silver phosphate is more pronouncedly yellow in colour and therefore more easily noticeable under these conditions. In presence of other metals such as iron etc. the aluminium should first be separated by addition of excess of sodium hydroxide for example and finally precipitated as hydroxide with ammonia.The precipitate after washing is dissolved in a slight excess of dilute sulphuric acid to form a solution suitable for the titration. The method gives good results even when only very small quantities of the metal are to be estimated. Improved Method for the Separation of Iron and Man- ganese. M. CARUS (Chem. Zeit. 1921 & 1194).-In the usual method for the separation of manganese from the metals of the iron group by precipitating the latter as basic acetates the con- tamination of the precipitate with manganese is not due to the co- precipitation of the basic acetate of this metal but to the formation of insoluble higher oxidation products owing to the action of dissolved oxygen.A perfect separation of the manganese in one operation even when a large excess is present is obtained by causing the precipitation with sodium acetate to occur in presence of a small quantity of hydrogen peroxide in which case no oxida- tion of the manganese salts can occur. The precipitate obtained after washing with dilute acetic acid containing a small quantity of sodium acetate and hydrogen peroxide and fhally with hot water is then completely free from manganese. G. F. M. I. &I. KOLT- HOFF and E. H. VOGELENZANG (Rec. truv. chim. 1921 40 681- 685) .-By reason of the hydrolysis of potassium chromate solution neither chromic acid nor dichromate can be neutralised using phenolphthalein as indicator. A study of the neutralisation of dichromate with sodium hydroxide leads to the following con- clusions :-Thymolphthalein should be used as indicator ; if phenolphthalein is used the solution must have been saturated previously with sodium chloride or barium chloride must be used to precipitate the chromate formed.The barium chloride may only be added when the solution is already yellow otherwise the precipitate of barium chromate contains chromic acid. It is claimed that the results are correct to within 0*2% but the method G. P. M. The Acidimetric Estimation of Dichromate. is not recommended owing to difficulGes with the indicator. H. J. E. Modified Method for the Estimation of Iron and Vanadium after Reduction by Hydrogen Sulphide. G. E. F. LUNDELL and H. B. KNOWLES ( J . Amer. Chem. Xoc.1921 43 1560- 1568).-The estimation of iron or of vanadium by reduction withANALYTICAL CHEMISTRY. ii 89 hydrogen sulphide followed by titration with potassium permah- ganate or dichromate ordinarily leads to high values. These high values are not due to the presence of sulphur and persist in spite of the complete expulsion of hydrogen sulphide and the avoidance of organic matter extracted from filter-paper. They may be ascribed to polythionic acids which are not destroyed by boiling in moderately concentrated sulphuric acid solution and are volatilised slowly from dilute and more rapidly from concentrated solutions. Reasonably accurate estimations may be made by restricting the volume of the original solution to 100 C.C. and pro- ceeding by the following modified process.The solution is acidified with sulphuric acid until it contains 2.5% sulphuric acid by volume reduced by hydrogen sulphide for thirty minutes in cold solution and for a further fifteen minutes during which the solution is raised to the boiling point. The hot solution is treated with 15 C.C. of 1 1-sulphuric acid and boiled for thirty to sixty minutes during which a stream of carbon dioxide is passed through until the total volume of liquid is about 50 C.C. The solution is cooled the current of carbon dioxide being maintained diluted to 200 c.c. and titrated with standard permanganate solution. In some cases it is advisable to filter off the separated sulphur after the hydrogen sulphide treatment. The filtrate is treated for a further ten minutes with hydrogen sulphide and the process completed as above.The average errors found by this method are for iron o'5y0 and for vanadium 0.1%. For accurate estimations of iron and vanadium in solutions containing platinum (as in rock analysis) a preliminary separation of the hydrogen sulphide group followed by expulsion of the gas complete oxidation with permanganate and reduction with sulphur dioxide is recommended. J. F. S. Estimation of Vanadium and Chromium in Ferrovanadium by Electrometric Titration. G. L. KELLEY J. A. WILEY R. T. BOHN and W. C. WRIGHT ( J . Ind. Eng. Chem. 1921 13 939-941) .-Three grams of the ferrovanadium are dissolved in a mixture of nitric acid and hydrochloric acid sulphuric acid is then added the mixture evaporated to expel all nitric acid and hydrochloric acid cooled and the solution diluted to 1000 C.C.One hundred C.C. of this solution are treated with 25 C.C. of sulph- uric acid (d 1-58) diluted to 300 c.c. boiled and 20 C.C. of 10% ammonium persulphate solution and 10 C.C. of o.2570 silver nitrate solution are added; the mixture is boiled for ten minutes 5 C.C. of hydrochloric acid (1 3) are then added the boiling is* continued for a further ten minutes the mixture treated with 26 C.C. of sulphuric acid cooled a t 5" and titrated with ferrous ammonium sulphate solution the end-point of the titration being determined electrometrically. This titration is a measure of the vanadium and chromium together. The vanadium is estimated by boiling 100 C.C. of the original solution with a few C.C. of ferrous sulphate solution adding 20 C.C.of sulphuric acid d 1.58 and 40 C.C. of nitric acid (d 1-40) diluting the mixture to 200 c.c. and boiling it a t such a rate that the volume is reduced to 100 c,c in one hour,ii. 90 ABSTRACTS OF CHEMICAL PAPERS. The solution is then cooled and titrated as before. The difference between the two titrations is a measure of the amount of chromium present. w. P. s. [Estimation of Antimony as Sodium Antimonate.] E. S. TOMULA (2. unorg. Chern. 1921 118 81-92).-See this vol. ii 74. Estimation of Bismuth. 0. A. CRITCIIETT (Eng. and Min. J. 1921 112 58).-A solution of the ore in a mixture of nitric and hydrochloric acids having been evaporated with sulphuric acid until fumes appear is diluted treated with a drop of hydrochloric acid filtered and the filtrate boiled with sodium thiosulphate and aluminium foil.The precipitate is collected returned to the beaker with hot water potassium hydroxide added and the liquid after having been boiled is filtered through the original paper. The latter with the precipitate is repeatedly evaporated with nitric and sulphuric acids until the paper is completely destroyed. After dilution boiling filtering addition of a slight excess of ammonium hydroxide and again boiling the precipitate is collected washed and dissolved in hot dilute nitric acid. The bismuth may then be estimated (a) as oxide after treatment with ammonium carbonate ( b ) as oxychloride after neutralising with ammonium hydroxide adding a little hydrochloric acid diluting and boiling or (c) by titration with permanganate after dilution treatment with ammonium oxalate boiling and separation with subsequent washing by decantation with hot water of the precipitate of bismuth oxalate.CHEMICAL ABSTRACTS. Analytical Chemistry of Tantalum Columbium and their Mineral Associates. I. The Use of Tartaric Acid in the Analysis of Natural Tantalocolwnbates. 11. The Separa- tion of Zirconium from Tantalum and from Columbium. WALTER RAYMOND SCHOELLER and ALAN RICHARD POWELL (T. 1921,119 1927-1935). Evaluation of the Degree of Unsaturation of Mineral Oils in the Bergius Process. H. I. WATERMAN and J. N. J. PERQUIN (Rec. truv. chim. 1921 40 677-680; cf. Dean and Hill Technical Paper 181 Bureau of Mines 1917).-Determination of the iodine number of an unrefined mineral oil before and after treatment by the Bergius process shows that it is a little greater after treatment.1%. J. E. Estimation of Phenanthrene. ARTHUR G . WILLIAMS ( J . Amer. Chem. Soc. 1921 43 1911-1919).-The phenanthrene is oxidised by iodic acid to phenanthraquinone which is precipitated as toluphenanthrazine by means of 3 4-tolylenediamine and weighed as such the procedure being as follows For materials containing 30% or more of phenanthrene 0.25 gram is weighed into a 50 C.C. conical flask 0.75 gram of iodic acid and 20 C.C. of glacial acetic acid are added and the mixture is boiled €or two and a half hours under an air condenser. After cooling forANALYTICAL CHEMISTRY. ii. 91 several hours any anthraquinone formed from anthracene present in the original material is filtered off on a Gooch crucible and washed with the minimum amount of glacial acetic acid.The filtrate and washings are evaporated to slightly less than 25 C.C. and then the volume is made exactly to 25 c.c. the mixture is cooled and 1 gram of 3 4-tolylenediamine is added and the flask left in run- ning water a t 20" over-night. The toluphenanthrazine is collected in a Gooch crucible and washed first with 25 C.C. of 50% acetic acid saturated with the phenanthrazine and then with 200 C.C. of cold water. The precipitate is dried and weighed and to the weight is added 0.053 gram to allow for the toluphenanthrazine remaining in solution in the 25 C.C. of glacial acetic acid. The factor for conversion into phenanthrene is 0.6052. Carbazole if present in amounts exceeding 10 yo interferes in the determination of phenanthrene and some of the high-boiling coal tar constituents interfere ; a crude anthracene cannot be directly analysed.For the detection of phenanthrene the material is oxidised as described above the mixture being cooled and filtered. The filtrate is poured into water and the precipitate collected and washed with water. The precipitate is warmed with concentrated sodium hydrogen sulphite solution and any residue is filtered off. The filtrate is washed in a separating funnel with one or two portions of carbon tetrachloride and then after the addition of a fresh portion of carbon tetrachloride is acidified with hydro- chloric acid containing ferric chloride. The carbon tetrachloride layer which contains the phenanthraquinone is separated and tested by Hilpert and Wolf's reaction (cf.A. 1913 ii 733) using a solution of antimony pentachloride in carbon tetrachloride a purplish-red precipitate being obtained on boiling if phenanthrene was originally present. W. G. Chemical Analysis of Caoutchouc Articles. ANDFA DUBOSC (Ann. Chim. Analyt. 1921,3 335-344).-A resume of the methods employed and the estimations necessary for a complete chemical analysis of caoutchouc and ebonite articles. (1) The acetone extract contains the natural resins added resins free sulphur oils and waxes and is evaporated to dryness and quantitatively examined for these substances by the usual methods. (2) The chloroform extract should be almost colourless. Brown coloration indicates the presence of tar or asphaltic adulterants.(3) The extract in alcoholic potash of the insoluble residue of the chloro- form extraction should not exceed 15% from a material con- taining about 50% of caoutchouc a larger proportion indicating added oils or fats. (4) The aqueous extract reveals the presence of starch or dextrins. (5) The estimation of total sulphur is best carried out by Henriquez's method as modified by the Bureau of Standards. (6) The ash is determined on the residue from the acetone extraction and a rough estimate of the caoutchouc content can be obtained by subtracting ash and total sulphur from 100. (7) None of the various methods which have been proposed for the estimation of caoutchouc itself give entire satisfaction. Theii. 92 ABSTRACTS OF CHEMICAL PAPERS.total foreign matter may be obtained however by solution in boiling nitrobenzene diluting with chloroform filtering through a tared filter washing with acetone drying and weighing. Estimation of Oxalic Acid in Urine. E. SALIIOWSKI (Biochem. Z . 1921 118 259-266).-A reply to Bau’s criticism of the author’s method (A 1921 ii 356). T. S. HAMILTON W. B. NEVENS and H. S. GRINDLEY (J. Biol. Chem. 1921 48 249-272).-Further improvements are made in the application of Van Slyke’s method to the estimation of amino- acids in feeding stuffs (cf. Eckstein and Grindley A. 1919 ii 204). Non-protein nitrogen is first removed from the material by suc- cessive extractions with anhydrous ether cold absolute alcohol and cold 1% trichloroacetic acid any protein removed by the latter being recovered by precipitation with colloidal ferric hydroxide.The main portion of the protein is then extracted with dilute (0.2%) sodium hydroxide. Starch is removed from the residue by treatment with hot 2% trichloroacetic acid and the remaining protein extracted by treatment first with boiling 20y0 hydrochloric acid and then with cold 5% sodium hydroxide. A small quantity of protein extracted with the starch is recovered by precipitation of the latter by addition of alcohol. The various fractions of protein thus obtained are hydrolysed with concentrated hydrochloric acid united and submitted to the Van Slykc analysis. The method is applied to oats corn cotton-seed meal and lucerne. J. SNAPPER and E. LAQUEUR (Arch. Nierl. Physiol.1921 6 48-57).-To 100 C.C. of urine 25 grams of sodium chloride are added and a litt’lc con- centrated hydrochloric acid. An aliquot portion is ext~actcd six times with ethyl acetate and the total extract is washed one(’ with one-quarter of its volume of water. The wash water is washed with an equal volume of ethyl acetate which is added to the original extract. After evaporation of the ethyl acetate the urea is decomposed by sodium hypobromite and the residual hippuric acid estimated by Kjeldahl’s method. The Rotation of Dextrose in Solutions of Trisodium Phosphate. Mutarotation as an Analytical Method. HANS MURSCHHAUSER (Biochem. Z. 1921 117 215-225).-The muta- rotation of dextrose is accelerated by trisodium phosphate. It follows a unimolecular law the velocity constants being also linear functions of the concentration of sodium phosphate.As the mutarotation is a function of the hydroxyl ion its use is indicated for distinguishing salts ol different alkalinity. Conditions Affecting the Quantitative Estimation of Reducing Sugars by Fehling ’s solution. Elimination of certain Errors Involved in Current Methods. P. A. QUISUM- BING and A. W. THOMAS ( J . Amer. Chem. XOC. 1921 43 1503- 1526).-The various sources of error in the current methods of G. F. M. H. K. Estimation of the Amino-acids of Feeding Stuffs. E. S. Estimation of Hippuric Acid in Urine. G. B. H. K.ANALYTICAL CHEMISTRY. ii. 93 using Fehling's solution are discussed. The inter-relationship of temperature 60-llO" and time of heating ten minutes to two hours to determine the best time and optimum temperature for reduction has been investigated.Fehling's solution has been studied from the point of view of the nature and concentration of the alkali concentration of copper sulphate and potassium sodium tartrate to find the maximum and minimum concentrations of these constituents necessary to give the greatest yield of cuprous oxide and to ensure the formation of $he complex cupric tartrate ion Auto-reduction of Fehling's solution a t different times and temperatures of heating has been measured showing those con- ditions under which absolutely no " blaiik " reduction is obtained. Conditions affecting the physical properties of the precipitated cuprous oxide the photosensitiveness and the keeping quality of Fehling's solution are recorded. A study of surface oxidation involving different methods of heating and vessels of various sizes has been carried out in order to determine the loss of copper due to surface oxidation and how to avoid it.The catalytic effect of the walls of the container has been demonstrated. A modified method of procedure for the estimation of sugars by means of Fehling's solution is described. In this method the solutions required are (1) copper sulphate solution containing 82.4 grams of CuS0,,5H20 per litre (2) alkaline tartrate solution; 376 grams of crystallised potassium sodium tartrate dissolved in water in a litre flask and the calculated amount of sodium hydroxide solution added to make 1 litre of this solution containing 130 grams of sodium hydroxide.The sodium hydroxide is made from material purified by alcohol which is kept in concentrated solution for several days to allow carbonates and other insoluble impurities to separate. To make an estimation 25 C.C. of the copper sulphate solution 25 C.C. of the alkaline tartrate solution and 50 C.C. of the sugar solution are placed in a beaker and warmed on a water-bath a t 80". After exactly thirty minutes the cuprous oxide is filtered on a Gooch crucible and washed. This may either be dried and weighed as cuprous oxide or dissolved in nitric acid and estimated electrolytically. From the weight of copper the amount of sugar may be obtained from tables which are given in the paper or by means of the following equations in which x is the amount in milligrams of copper obtained from y mg.of sugar dextrose y=0.474~+0*0001 15x2 ; lzvulose y=0*526x+ 0.000078~~ ; lactose y=0*813~+0~000003x~ ; maltose y=O*99Ox+ 0*0000005~~ ; and invert-sug?r y=0~504~+0~0000870x~. This method is designed for use in the analysis of saccharine materials containing sucrose dextrose lavulose invert-sugar lactose and maltose. It is not claimed that the method can be used for the accurate quantitative estimation of 0.1 % or less of invert-sugar in approximately pure sucrose. J. F. S. Errors in the Estimation of Sugar by Fermentation with Yeast. CARL LANCE (Berlin Klin. Woch. 1921 58 957-959; from Chem. Zentr. 1921 iv 848).-The estimation of sugar inii. 94 ABSTRdCTS OF CHEMICAL PAPERS. urine by fermentation with yeast is subject to certain errors.The evolved gas is not entirely carbon dioxide but contains also nitro- gen from the reaction of carbamide ammonia or amino-acids with nitrites. The latter may be formed by reduction of nitrates in the urine or may occur in the yeast. There may also be an evolution of carbon dioxide from carbonates present in the urine. Errors may be diminished to some extent by sterilisation and precipitation of carbonates with calcium chloride. The estimation of sugar in urine however gives only an approximate value. G. W. R. Limitations of the Modified Lewis-Benedict Method of Blood Sugar Estimation. RUTH A. GUY (Biochem. J. 1921 15 575-576).-0*0001 Gram of acetone added to 2 C.C. of blood produces an observable colour change in Lewis and Benedict's picric acid method of sugar estimation (A.1915 ii lll) but no change is noted with similar quantities of acetoacetic acid. G. B. The Catalytic Power of Flour. 0. FERN~DEZ and A. PIZARROSO (Anal. Fib. Quim. 1921 19,. 265-268).-The catalytic activity of flour measured by its decomposition of hydrogen peroxide has been proposed as a mea'sure of its grade of extraction. The results obtained by the authors using samples of flour of different origin showed no correlation between catalytic activity and total- or phytin-phosphorus. The test is held to be of little value. G. W. R. Identification of Oxycellulose by means of the Barium Compound. ERNST BECKER (ZelZstoSf u. Papier 1921 1 5-7).-When 2 grams of oxycellulose are shaken with 50-60 C.C. of barium hydroxide solution for four hours and the insoluble portion is washed with water until the filtrate is free from barium compounds a barium compound of oxycellulose remains of which the content of barium varies according to the origin of the oxycellulose. CHEMICAL ABSTRACTS.Benzidine Hydrochloride as a Reagent for Wood Cells. C. VAN ZIJP (Pharm. Weekblud 1921 58 1539-1542).-A solution of 0.2 gram of benzidine in 19 C.C. of water to which 1 C.C. of 25% hydrochloric acid has been added gives an orange stain to ligneous matter in microscope sections. Sections of material containing tannins or acids which act on iron should be washed free from iron with a 1% solution of hydrochloric acid in alcohol after cutting. Starch can be stained with iodine in the same section without interfering. The reagent also detects diseased tissues in Hevea bark and for this reason as well as because oPits cheap- ness as compared with phloroglucinol is of great use for control on rubber plantations.Detection of Formaldehyde with Phenols. B. PFYL G. REIF and A. HANNER (C'hem. Zeit. 1921 45 1220-1221).- Phenol reactions for the detection of formaldehyde as previously carried out (cf. A. 1921 ii -663) are not sufficiently trustworthy s. I. L.ANALYTICAL CHEMISTRY. ii. 95 when the test is to be adapted to the detection of methyl alcohol in potable spirits and tinctures after distillation with permanganate as colour reactions are often simultaneously given by the traces of other aldehydes alcohols etc. which pass over into the dis- tillate and the mixed colours produced allow of no certain con- clusions being drawn.A solution of guaiacol or of upomorphine hydrochloride in concentrated sulphuric acid (0.02 gram in 10 c.c.) gives however a reagent with which a sharp distinction can always be observed if methyl alcohol is present in the original tincture. The reaction is best carried out by adding a few drops of the distillate to 0.5 C.C. of the reagent in a watch glass. With the guaiacol reagent a clear dark red colour is produced when formalde- hyde is present which is readily distinguished from the pale yellow coloration produced in its absence whilst with the apomorphine reagent a characteristic precipitate is formed in presence of form. aldehyde. As little as 025% of methyl alcohol in tinctures etc. can be detected with certainty by the new method.ED. JUSTIN-MUELLER (J. Pharm. Chim. 1921 [vii] 24 334-336).-As little as 1 part of furfuraldehyde in 600,000 parts of solution may be detected by the blue coloration which is obtained when 5 C.C. of the solution 5 C.C. of hydrochloric acid and 0.02 gram of orcinol are heated G. F. 11. Orcinol Reaction of Furfuraldehyde. together cGoled and shaken with a few-drops of amyl alcohol. w. P. s. Source of Error in Tests for Acetone. E. PITTARELLX (PoZicZinico 1921 28 621; J . Am. Med. ASSOC. 76 1803).- Caoutchouc under the influence of steam or boiling water yields a volatile substance which responds to all the tests most character- istic of acetone ; therefore conclusions based on technique involving distillation in the presence of caoutchouc may be misleading. CHEMICAL ABSTRACTS.Microchemical Reactions of “ Dulcin ” [p-Ethoxyphenyl- carbamide]. G. DENIGI~S and R. TOURROU (Compt. rend. 1921 173 1184-1186).-When a few particles of “ dulcin ” on a microscope slide are moistened with one drop of nitric acid (d 1.39) tlhey dissolve and on the addition of a drop of water microscopic orange OF brick-red crystals of p-ethoxynitrophenylcarbamide are obtained. These crystals are soluble in chloroform and on evaporation after the addition of a drop of acetic acid character- ist8ic crystals are obtained. If dilute nitric acid is used in place of the concentrated acid the “dulcin ” does not dissolve but the mass gradually becomes permeated with crystals of the nitro- compound and under the microscope there is the appearance of a marked effervescence.“ Dulcin ” is soluble in concentrated sulphuric acid or glacial acetic acid and is deposited as a micro- crystalline precipitate from such solutions on the addition of water or alkali. W. G. The Vitali Reaction for Cocaine. PAUL HARDY ( J . Pharm. Chini . 1921 [ vii] 24 325-330) .-Pure cocaine snd most sub-3. 96 ABSTRACTS OF CHEMfCAL PAPERS. stituted cocaines yield a yellow coloration with the Vitali test in the cold ; isoatropylcocaine however yields a violet coloration and the presence of a small quantity of this substance in certain specimens of cocaine causes these to give a violet coloration with the test. When the reaction mixture is heated pure cocaine Morphine Codeine and Narcotine in Indian Opium. JITENDRA NATH RAKSHIT (AnaZyst 1921 46 481-488).-The morphine content of the bulk of Indian opium is between 8.5 and 10.5y0.The B.P. process for estimating morphine is inefficient in India owing to the high temperature which prevails. The U.S.P. process is better and compares favourably with the author's polarimetric process (Analyst 1918 43 321). The solubility of codeine and narcotine has been determined in various solvents a t temperatures between 20" and 100". Methods have also been worked out for the estimation of codeine and narcotine for which the original should be consulted. Estimation of Tannin and Colouring Matters in Wines. W. FRESENIUS and L. GRUNHUT (2. anal. Chem. 1921 60 406- 417).-One hundred C.C. of the wine is evaporated to expel alcohol cooled diluted to 100 C.C. and 50 C.C. of this solution are treated with a few grams of pure animal charcoal; after some hours the mixture (a furthhr quantity of charcoal must be added if all the colour has not been removed) is diluted to 1 litre filtered and 400 C.C. are diluted to 1 litre treated with 10 C.C. of sulphuric acid (d l*ll) and 30 C.C. of indigo solution (3 grams of indigo dissolved in 20 C.C. of sulphuric acid and diluted to 1 litre) and the mixture is titrated with permanganate solution. Twenty C.C. of the de- alcoholised wine not treated with charcoal are titrated in a similar manner. The difference between the two titrations is a measure of the tannin and colouring substances in the wine. The permanganate solution should contain 1.33 grams of potassium permanganate per litre and be standardised against 10 C.C. of N/lO-oxalic acid solution ; the volume of permanganate solution used is divided into 0.0416 to obtain the tannin value of 1 C.C. of permanganate solution. Determination of the Size of Particles. Attempts to Explain the Formation of Layers in Clay Turbidities and their Use in Soil Analysis. ERNST UNGERER (KoZZoid Chem. Beihefte 1921 14 63-95).-The layers in clay suspensions are brought about solely by the size and weight of the suspended particles so that each layer corresponds with particles of a definite size. The turbidity between two layers contains particles uniformly dispersed. Layers are formed both in solutions containing electro- lytes and in solutions which do not contain electrolytes but a high concentration of a coagulating electrolyte will probably prevent the formation of layers. The individual layers either rise or fall with a uniform velocity and from the rate of falling or rising the size of the particles in a given4ayer may be calculated by means of Stokes's law. produces a t most a slight yellow coloration. w. P. s. H. K. w. P. s. J. F. S.

ISSN:0368-1769    

DOI:10.1039/CA9222205077

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

PIIYSIOT,OC~TCATJ CHEMISTRY. i. 79 Physiological Chemistry. Subcutaneous Absorption of Oxygen in Mountain Climbing and Aviation. RAOUL BAYEUX (Compt. rend. 1921 173 937- 939) .-The resistance to subcutaneous injection of oxygen diminishes as the height increases in the ascent of a mountain. That this is not due to the fatigue of climbing is shown by experiments conducted in a decompression chamber. In the latter experiment the de- crease in resistance was accompanied by a slight increase in the beat of the pulse and a very slight increase in the velocity of respir- ation. The reverse process occurs as the altitude decreases or the pressure in the chamber increases. The injection of oxygen was not accompanied by formation of a gaseous turnour and the oxygen was rapidly absorbed.W. G. Influence of Temperature on the Reaction of the Blood. JOSE M. DE CORRAL (Biochem. Z. 1921,117 1-9).-The reaction of blood a t 38" is P,=0.22 lower than a t 18" in agreement with Michaelis and Davidoff's findings (A. 1912 ii 1184) provided that the blood is in equilibrium with carbon dioxide at 38" and then measured a t 18". If the blood is in equilibrium with carbon dioxide a t both temperatures then the P is independent of tem- perature as found by Hasselbalch (A. 1917 i 490). The results with serum still show discrepancies. H. K. Excretion of Sweat and the Composition of the Blood. EBERHARD WILBRAND (Biochem. Z. 1921 118 61-66).-Heavy perspiration is followed by a thickening of the blood; parallel with this there is a loss of protein and sodium chloride from the serum.The residual (non-precipitable) nitrogen of the blood and the content of fat are unaltered. Concentration of the Blood. 11. The Action of Diuretics of the Purine Group on the Exchange of Substances between the Tissues and the Blood. W. NONNENBRUCH (Arch. expt. Prrth. Pharm. 1 921 91 332-341 ) .-Theophylline theocine and H. K.i. 80 ABSTRACTS O F CHEMICAL PAPERS. euphylline cause the blood to lose water which is soon replaced. The serum proteins increase often to a very large extent not only relatively but absolutely and this stream of protein from the tissues into the serum even occurs after extirpation of the kidneys. An Effect of the Ingestion of Colostrum on the Composition of the Blood of New-born Calves. PAUL E. HOWE ( J . Bid.Chem. 1921 49 115-118).-The blood of the new-born calf does not contain euglobulin or pseudo-globulin I but after ingestion of colostrum relatively large amounts of these proteins are present. If no colostrum is given they are only formed slowly. The function of colostrum seems to be to supply them rapidly. Calcium Content of Blood Plasma and Corpuscles in the New-born. MARTHA R. JONES ( J . Biol. Chem. 1921 49 187- 192).-The whole blood contains 8.8 mg. the corpuscles 5-0 mg. the plasma 12.3 mg. of calcium per 100 C.C. The average for plasma is higher and for corpuscles and whole blood less than for older children. In the-first twelve days of life the average percentage of red cells dropped from 55 to 42%. Action of Pilocarpine on the Composition of the Blood. A.BORNSTEIN and ROBERT VOGEL (Biochem. Z. 1921,113 1-14). -Pilocarpine administered to dogs alters the distribution of water in the body the blood showing increased content of hEmoglobin corpuscles and serum proteins. This change is only partly to be attributed to excretion of water from the body. I n addition pilocarpine produces hyperglyczmia in dogs and rabbits. Extir- pation of the pancreas has no inhibiting action on these results but atropine is antagonistic to all. Biood and Metabolism Studies with Radium Emanations. J. HAUENSTEIN (&lunch. med. Woch. 1921 68 809-810; from Chem. Zentr. 1921 iii 795).-Observations were made of the effect of radium radiations on the numbers of red and white blood corpuscles and on the behaviour of the individual leucocyte forms in cases of carcinoma of the uterus.Red corpuscles disintegrate and decrease in amount under the influence of 7-rays. Leucocytes increase in number. There is a relative and absolute increase in neutrophiles and a relative although not absolute decrease in lymphocytes. No effect was observed on the large white blood cells and the mononuclear eosinophile and basophile cells. The metabolism experiments showed that the nitrogen content of the urine decreased markedly during and after treatment. Similar results were obtained for uric acid. Acetone and aceto- acetic acid were not found. The figures for iiidican were abnormal and slight albuminuria was observed. Permeability of the Red Corpuscles of Human Blood for Anions. ERNST WIECHMANN (P’iiger’s Archiv 1921 189 109- 125; from Chem.Zentr. 1921 iii 895).-In native human blood the chlorine ion is distributed between corpuscles and plasma in G. B. G. R . G. B. H. K. G. W. R.PHYSIOLOGICAL CHEMISTRY. i. 81 the ratio 1 2.1. This distribution is unaltered by isotonic sodium chloride solution. In the presence of sodium sulphate solution chlorine ions pass out from the corpuscles. The partition ratio between corpuscles and suspending liquid is found to be 1 19.7 for the sulphate ion 1 9.7 for the phosphate ion and 1 3.1 for the bromine ion and the chlorine ion under similar conditions of experiment. The permeability for the phosphate ion increases with the temperature. Permeability for the bromine ion is de- creased by the presence of calcium. “ Cyanol,” “ light green- F.S,” ‘< setopalm,” and ‘< ponceau 2R ’’ were scarcely absorbed after two hours.G. W. R. Quinine Ksmolysis. ALFRED LUGER (Biochem. Z. 1921 117 145-1 52) .-When treated with quinine blood corpuscles show a diminished resistance to acids and an increased resistance to alkalis. In the presence of saline solution such corpuscles show a diminished resistance to water but an increased resistance to saponin. H. K. The Amino-acid Content of Plasma and Corpuscles accord- ing to Bang. A. COSTANTIKO (Biochem. Z. 1921 117 140- 144).-Polemical against I. Bang (cf. A 1916 i 528). Normal Sugar Content of the Blood. P. J. CAMMIDGE J. A. C. FORSYTH and H. A. HOWARD (Brit. Med. J. 1921 ii 586- 59O).-As the result of observations on the blood-sugar of man and animals the authors hold the view that the liver contains a diastatic ferment the action of which is reversible.I n the fasting state the glycogenolytic activities of this enzyme are largely inhibited by mi anti-ferment formed by the pancreas the im- permeability of the resting liver cells to sodium chloride and the reaction of the blood and liver cells. After the taking of food when acids enter the duodenum the secretion formed stimulates the liver cells to produce bile thus permitting the entrance of sodium chloride which activat’es the diastatic ferment. At the same time it causes a secretion of alkaline pancreatic juice which combines with the acid gastric contents forming acid salts and sodium chloride which pass to the liver and increase the activity of the diastatic ferment.It also interferes with the formation of the internal secretion of the pancreas thus diminishing its inhibitory effect on glycogenolysis in the liver. Carbohydrates reaching the liver from the intestine or formed from proteins in the liver are converted into glycogen by the diastatic ferment the efficiency of the process depending on the extent to which the glycogenolytic action of the enzyme is inhibited by the internal secretion of the pancreas. Unless the power of glycogen formation possessed by the liver is exceeded sugar as such or formed from starch in the intestine does not pass into the general circulation or play any direct part in the rise of blood-sugar following food. Lactic Acid in the Blood of Dogs in Exercise. A. B. HASTINGS (Proc. Xoc.Exp. Biol. Med. 1921,18 306-307).-Severe exercise of short duration increases the lactic acid but prolonged H. K. G. B.i. 82 ABSTRACTS O F CHEMIC.41 P,4PEERS. moderate exercise decreases it. The significance of lactic acid as a primary factor in physiological fatigue not carried to exhaustion seems t o be an open question (cf. similar results in man Ryflel -4. 1910 ii 325). G. B. Distribution of Uric Acid in the Blood. R. C. THEIS and S. R. BENEDICT ( J . Lab. Clin. Med. 1921 6 680-683).-Uric acid was estimated in plasma and corpuscles in 104 cases 51 of which showed equal distribution 45 showed plasma uric acid greater than corpuscle uric acid and 8 thc (miverse. This rela- tionship holds for osalazted and defibrinztcd blood and does not G. €3. Use of Frogs to Demonstrate the Anticoagulating Action of Nucleic Acids.DOYON (C'ompf. rend. 1921 173 1120- 1122).-The frogs are clccapitated aiid sixty drops of their blood allowed to drop into 0.5 C.C. of a solution containing 0.0033 gram of nucleic acid 0.0025 gram of sodium carbonate aiid 0.002 gram of sodium chloride. No coagulation occurs. Other experiments Changes in the Blood after Oral Administration of Sodium Chloride. G . SAMSON (Biochem. Z. 1921 118 65-60).-0ral administration of sodium chloride is f ollo~vecl by increased sodium chloride content of the blood-serum the rnaj or portion however passing into the tissues. There is also an iiicrcase of the protein content of the blood. depend on pathological conditions. with frogs are described. IT. G . H. K. Are there Protective Enzymes against Polysaccharides ? EMIL AEDERHALDEN (Biochem. Z.1921 147 161-165).-Mainly polemical against Herzfeld and Klinger (cf. A. 1921 i 286). H. K. The Fate of some Polysaccharides in the Digestive Tract of Mammals. TOMIHIDE SHINIZU (Biochem. Z. 1921 117 227-240).-F~cal constituents are able to convert inulin lichenin and hemicellulose into acetic propionic and butyric acids. Lactic acid also appears. The agent is probably bacterial as pure cultures for example Bacillus coli B. lactis B. proleus and B. subtilis have the same power. Hydrolysis of some Polysaccharides (Inulin Eichenin and Hemicellulose) in the Digestive Tract of Mammals. TOMI- HIDE SHIMIZU (Biochem. Z . 1921 117 241-244).-Macerated gut or pancreas separately or combined failed to liquefy or produce reducing sugars from thc polysaccharides named.Cellulose Fermentation in the Paunch of the Ox and its Importance for Metabolic Experiments. W. KLEIN (Biochem. Z. 1921 117 67-68).-A criticism of Krogh and Schmit-Jensen's results ( J . Physiol. 1921 Sept. 20) on the carbon dioxide-methane ratio chiefly on t{he grounds of priority. H. K. H. K. H. K.Basal Metabolism of Underweight Children. KATHARINE BLUNT ALTA NELSON and HARRIET CURRY OLESON (J. Biol. Chem. 1921 49 247-262).-The basal metabolism tends to be (up to 40°/,) higher than in the normal child. Variations in Chloride-metabolism Due to Menstrual Processes. W. EISENRARDT and R. SCI-IAEFER (Biochem. Z . 1921 118 34-%).-As a rule immediately before or during the menstrual period there is an increased content of chloride in thc circulating blood as estimated by Bang's micro-method. Calcium and Phosphoric Acid Metabolism with Large Doses of Calcium and Sodium Phosphate.K. BLUHDORN (Z. Kinclerheilk. 29 43-55; from Chem. Zentr. 1921 iii SSS).- No harmful effects followed the administration of large quantities of calcium. A portion of ihe calcium given as chloride or lactate is probably retained but the greater part is excreted in the faxes. The phosphoric acid exchanges run parallel with the calcium exchanges. Addition of sodiizni phosphate increases the retention of calcium. When calcium chloride is adrninistercd it is appar- H. STAUB (Biochem. Z. 1921 118 93-102).-There is a diminished capacity for assimilating the first dose of dextrose in fasting persons or after a diet of fat and protein and also after hard work.I n :t fasting person the assimilation increases to a maximum after ten hours and then falls off after fifteen or more hours. To explain these and other results " equilibrating ferments " (Gleichgewichts- fermente) are postulated as produced in the blood by foodstuffs to restore to equilibrium the sudden abnormal conditions produced Influence of some Polysaccharides (Inulin Lichenin and Hemicellulose) on Protein Exchange. TonmiIDE SRIMIZU (Biochem. Z. 1921 117 245-251).-Peeding experiments on dogs show that the polysaccharides named have a protein-sparing action. H. I<. The Fate of Parenteral Administered Sulphur and its Influence on Metabolism. ROBERT MEYER-BISCH and E. BASCH (Biochein.Z . 1921 118 3949).-Intramuscular injec- tion of sulphur in oil is followed by increased protein breakdown shown by increased nitrogen and sulphur output in the urine tJhe proportion of the latter element being greater than that adminis- tered. H. K. Antiketogenesis. 111. Calculation of the Ketogenic Balance from the Respiratory Quotients. PHILIP A. SHAFFER (J. Biol. Chem. 1921 49 143-162; cf. A. 1921 i 754).-The author makes the following assumptions (not wholly justified by experiment). (1) Each molecule of fat gives 3 molecules of aceto- acetic acid and 0-5 molecule of dextrose or its equivalent anti- ketogenic derivative. (2) Protein is convertible ( a ) ' into anti- ketogenic dextrose or its equivalent to the estenl of 3.6 grams G . B. H. K. mtly retained as such at first.G. w. R. Facilitation of Intermediary Sugar Metabolism. by a high concentration of the food administered. H. K.i. 84 ABSTRACTS OF CHEMICAL PAPERS. for each gram of urine nitrogen ( b ) into acetoacetic acid for each molecule of leucine phenylalanine and tyrosine it being calcu- lated that each gram of urine nitrogen corresponds with approxi- mately 10 millimols. of ketogenic substance. ( c ) Valine lysine histidine and tryptophan are neutral as to ketogenesis. (3) Carbo- hydrate exerts its antiketogenic function in the form of dextrose 1 gram of which is therefore equivalent to 1000/180=5.56 millimols. of antiketogenic substance. A method is described by which the ratio of Betogenic to anti- ketogenic molecules in the metabolic mixture can be calculated from the respiratory quotient.The molecular ratio 1 1 corre- sponding according to the calculation with a respiratory quotient of 0.76 appears to be the limit for the avoidance of acetone sub- stances. With a quotient > 0.76 the katabolism of the antiketogenic dextrose or its equivalent from protein and glycerol is great enough to remove aceto-acetic acid as fast as it is formed. G. B. The Minimum of Odour Perceptible in an Absolutely Inodorous Space (Camera Insdorata). K. KOMURO (Arch. Ne'er,?. Physiol. 1921 6 20-24).-The camera is a large glass box which can be made inodorous by means of a mercury vapour lamp and into which the head of the experimenter can be introduced. Inside this chamber the minimum necessary for perception of a number of odours is 20-25% less than outside that is the nose becomes more sensitive when all other odours are eliminated.G . B. Acid Taste. WOLFGANG OSTWALD and ALFRED KVPIN (KoZEoid Z. 1921 29 266-271).-The connexion between the acid taste and the power of producing swelling is considered. It is shown that neither quantity is strictly proportional to the free hydrogen-ion concentration nor is this quantity in any way a quantitative measure of either. The stronger the swelling action of an acid the greater the hydrogen-ion concentration must be before an acid taste is detectable. Consequently swelling action and acid taste are directly opposed to one another. Strongly swelling acids taste less acid than weakly swelling acids of the same hydrogen- ion concentration. The series of minimum hydrogen-ion concen- trations which can be detected by taste and the series of swelling constants do not run parallel for the 13 acids examined but may be connected by means of an experimental equation which contains two constants.Acid salts and buffer solutions exhibit the above- named relationship between acid taste and swelling power. Xolu- tions of these substances taste much more acid than solutions of their acids of the same hydrogen-ion concentration. This is in keeping with the colloid-chemical rule that the addition of salts reduces the swelling power of acids. A tentative hypothesis is put forward that the acid taste is qualitatively due t o the hydrogen ion but quantitatively to the simultaneous swelling action of the colloids in the region of the nerve-endings which is not determined by the hydrogen-ion concentration J.F. S.PHYSIOLOGICAL CHEMISTRY. i . 85 Chemical Constituents of the Egg of the Common Frog (Ram temporaria) and their R6le in its Embryonic Develop- ment. E. FAUR~LFREMIET and (MLLE) Du VIVIER DE STREEL (Bull. SOC. Chim. Biol. 1921 3 476482).-The ripe egg has the following composition water 57.60y0 glycogen 3.31 yo lipoids 10*14% vitellin tablets 26.51 yo the remaining 2.44% consisting of pigment nucleus and cytoplasma. The vitellin tablets which are partly soluble in alkalis contain phosphorus nitrogen and sulphur. E. S. Constitution of the Egg of Sabellaria alzeolata L. E. FAURg-E(REMIET (Cmnpt. rend. 1921 173 1023-1026).-The eggs of Sabellaria alveolata L. contain 70% of water; lOG3% of protein; 6.80% of fatls and lipoids; 1.27% of glycogen and 1.53% of ash.The protein fraction consists of two distinct substances one slightly acid the other neutral. The fatty substances in the eggs exist in three principal forms namely neutral fats soaps and Tetrodon Poison and some of its Chemical Characteristics. I?. ISHIHARA ( T ~ k y i i Igakukai Zasshi 1917 31 1-39).-The poison which was extracted from eggs of the globe fish is a taste- less white powder containing sulphur and an amino-group; it gives a positive ninhydrin reaction and a positive reaction for creatinine. phosphatides. w. G . Dextrose is present probably as a dextrose ester. CHEMICAL ABSTRACTS. The Chemical Composition of Brain. TOMIHIDE SHIMIZU (Biochem. Z . 1921 117 252-262).-From 35 kilos.of ox-brain fractions of a gram of most of the amino-acids were isolated together with purine and pyrimidine bases and choline. Non- nitrogenous constituentls identified were succinic acid d-lactic acid and inositol. H. K. The Calcium-Potassium Action. K. SPmo (Schweix. med. Woch. 51 457-460; from Chem. Zenir. 1921 iii 8S8-%39).- Examples are given of the antagonistic physiological action of calcium and potassium. With isolated frogs’ hearts poisoning by potassium salts was neutralised by calcium salts. The effect of certain alkaloids nzsy be influenced by the relative amounts of calcium and potassium present. Changes in the reaction of the medium influence the calcium-potassium action. Choline as Hormone for Intestinal Movement. 111. Participation of Choline in the Action of Various Organic Acids on the Intestine.IV. Effect sf Choline on Normal Gastric Movement. J. W. LE HEUX (P’iiger’s Archiv 1921,190 280-300 301-310; cf. Ann. Report 1919 16O).-III. The effect on the isolated intestines of salts of various organic acids is explained as being due to the formation from these acids of esters of choline from the choline present in the walls of the bowel with the aid of it synthetic enzyme which is also there. The activity of these esters compared with choline as estimated by the contractioa G. W. R.i. $6 ABSTRACTS OF’ CHEMlCAT PAPERS. produced is Acetic ester 1000 propionic 300 formic 100 n-butyric 40 isovaleric 15 benzoic 2 succinic 1. The sodium salts of the acids have no effect if the intestine is first freed from choline by washing; in some cases the further addition of choline or of the washings restores thc effect.Atropine antagonises the effect of these salts as it does t,hn.i of choline. The possibility that the stimulating effect of sugars on the intestine may be due to inter- mediate formation of it pyruvic ester is discussed. IV. X-Ray observations on cats showed that 4-10 mg. of choline chloride given intravenously nccelerabes the movements of the stomach and small intestine. G. €3. Benzoate Administration and Hippuric Acid Synthesis. G. D. DELm-ur and G. H. WHIPPLE ( J . Biol. Chern. 1921 49 229-846).-A severe liver injury for instance extensive necrosis due to chloroform delays but does not prevent t,he synthesis of hippuric acid. The authors attribute the synthesis in these cases to the subsidiary ttctJion of other cells of the body.The intravenous administration of benzoate always increases ammonia urea and total nitrogen of the urine. Under certain conditions benzoate injection causes a considerable breakdown of protein due probably to the acute need of glycine. The Part Played by Acid in Carbohydrate Metabolism. IV. The Relation between Acid and Alkali and Adrenaline- glycosuria. H. ELIAS and U. SAMMARTINO (Biockem. Z. 1922 117 1 0 4 0 ; c€. A. 1919 i 54).-Glycosuria induced by injection of acids into rabbits does not cause congestion of the liver sucli as occurs in piqQre or adrenaline glycosuria. There is marked acidosis produced in rabbits by subcutaneous administration of adrenaline the lactic acid content of the liver increasing threefold.The mobilisation of sugar produced by adrenaline in isolated tortoise liver is inhibited by alkali but rcstored by neutralisation. Liver Function. G. B. H. K. Energy Exchanges in Muscle. IV. Formation of Lactic Acid in Cut Muscle. OTTO MEYERHOF (E‘jliiger’s Archiz; 1921 188 114-160; from &‘hem. Zentr. 1921 iii 892; cf. A. 1921 i 76).-In the estimation of lactic acid in frog’s muscle the material is extracted directly with 967& ethyl alcohol. The extract is evaporated to dryness and the residue ground and washed with saturated sodium sulphate solution. The lactic acid maximum observed in cut muscle is attributed to inhibition of its production owing to increase of acidity. By varying the conditions the whole of the glycogen map be changed into lactic acid.Addition of dextrose hexosephosphoric acid or glycogen to muscle sus- pended in a phosphate solution does not increase the rate of for- mation of lactic acid if the addition takes place in the f i s t hour. Disappearance of lactic acid runs parallel with oxidation. Whilst under anaerobic conditions there is an equivalence between the disappearance of carbohydrate and the formation of lactic acid the equivalence of the reverse process does not hold for cut muscle.PHYSIOLOGICAL CHEPtiISTRY. i. 87 A correlation exists between respiration intensity and lactic acid formation. In cut muscle respiration intensity is nearly equal to the maximal respiration intensity for uncut muscle. The Oxidative Degradation of Dextrose in the Animal Body. JULIUS HIRSCH (Biochem.Z. 1921 117 113-116).-By use of dimethylhydroresorcinol (dimedon) as a fixative for acetaldehyde the presence of acetaldehyde in 900 grams of frog's muscle was detected by isolation of 0.3 gram of condensation product (aldomedon). H. K. Fixation of Lime by Animal Tissues. 111. E. PREUDEN- BERG and P. GYORGY (Biochem. z. 1921 118 50-54; cf. A. 1921 i 382).-Cartilage which has absorbed the alkaline-earth metals has also the power of fixing phosphate. The colloids of the cartilage are assumed to play a part in khis chemical combination. G. W. R. H. K. Zinc in the Human and Animal Organism. E. ROST (Med. Klin. 1921,17,123-124).-1n the human body zinc is to be found in almost all organs and tissues particularly in the liver and in the muscles.I n the liver of infants there is 39-82 mg. per kilo. of tissue in adults 52-145 mg. per kilo. Zinc is present in the secretions (milk urine faxes) and in epidermal structures such as hair. Human milk contains 1.3-1.4 mg. per litre; goat milk 2.3 mg.; cow milk 3.9 mg. I n the urine 0.6-1.6 mg. and in the feces 3-19 mg. are eliminated daily. Hair contains 9 mg. per kilo. The zinc is derived largely from the meat eaten but some is taken in as vegetable matter. In the tissues the zinc exists in a more or less firm union with protein. The Measurement of the Influence of Heat and Light on the Activity of Reduction of Animal Tissues and Applica- tions to Heliotherapy. S. VALLOT (Compl. rend. 1921 173 1196-1 198).-The rate of reduction of inethylene-blue by animal tissues is markedly increased by rise in temperature or by an increase in the intensity of the iIIumination and the beneficial therapeutic effects of solar radiation are attributed to tlhis increased activity of reduction.W7. G. GUSTAV I I ~ A R D and ROBERT FILLON (Compt. rend. 1921 173 935-937).-The oil extracted from fresh starfish has d15 0-9372; n22 +47" (Amagat and Jean); brismer index 48"; iodine value (Wijs) 132.7; saponi- Inorganic Constituents of Milk. I. Chlorides in Human Milk. W. R. SISSON and W. DENIS (Amer. J . Dis. Children 1921 21 389).-The average chloride content of all specimens examined was 58.2 mg. C1 per 100 C.C. It is higher in the first weeks of lactation and after the second week the average is 52.6 mg. C1 per 100 C.C.CHEMICAL ABSTRACTS. The Chemical Composition of Starfish. fieation value 159.1 ; unsaponifiable matter 38.94%. w. G. G. B.i. 88 ABSTRACTS OF CHEMICAL PAPERS. The Alkaline Tide ” after Meals. I. CYRUS H. FISKE ( J . Biol. Chem. 1921 49 163-170).-The author lays stress on the P of the urine rather than on titration values. The influence of the food taken renders the interpretation of small variations of PH uncertain but after a full meal an undoubted increase in alkalin- ity occurs quite suddenly in the second or third hour. Inorganic Phosphate and Acid Excretion in the Post- absorptive Period. CYRUS €1. FISKE ( J . Biol. Chem. 1921 49 171-181).-During the night the rate of excretion of inorganic phosphorus in the urine is greater ( l g times to twice) than during the day.This the author attributes to retention of phosphorus in the morning. The rate of phosphate excretion is to some extent parallel to the hydrogen-ion concentration but does not wholly account for the variatlions in the latter (cf. preceding abstract). G. B. G. B. The Iodine Number of Urine. OSKAE WELTMAEN (Wiener Arch. inn. Ned. 1921 2 107’-120).-The affinity of urines for iodine normally varies directly with the density and inversely with the amount of the urine. The amount of iodine with which 100 C.C. of urine combines is termed the “percentage iodine number,” and the corresponding amount for twenty-four hours the “ absolute iodine number.” When the iodine number and the density show wide variation a relatively high iodine number indicates extra-renal factors and a relatively low iodine number a severe injury to the kidney.High iodine numbers have been noted in certain diseases of the liver acute febrile conditions and certain rapidly progressing malignant neoplasms. CHEMICAL ABSTRACTS. Amino-nitrogen in the Urine by the Formol Method. C. CIACCIO (Arch. Sci. med. 1920 43 177-181).-This nitrogen is considered to be present not as amino-acids but as polypeptides. This conclusion is based on a comparison of results by the Henriquez method and those obtained by a preliminary treatment with mercuric acetate or by tannin and lead acetate. Quantitative Measurement of the Transient Excretion of Caffeine in Man by a New Biological Method. EDUARD FRIEDBERG (Biochem. Z. 1921 118 ICi4--284).-The method depends on the observation that there is a sharp contraction of the transversely striped musculature of the frog a t a concentration of caffeine of 1 in 3,600. The caffeine in urine is isolated from the dried residue by extraction with chloroform.In man diuresis is not solely dependent on the dose of caffeine but partly on the water content of the tissues. The cessation of excretion of caffeine is early possibly due to degradation of the caffeine to a methyl- xanthine. The smallest proportion of caffeine taken by the mouth and recognisable in the urine is 10 mg. A Red Colouring Matter Produced by the Action of p-Dimethylaminobenzaldehyde on Normal Urine. PAT~L HBRI (Biochem. Z. 1921 117 41-64).-When p-dimethylamino- G. B. H. K.PHYSIOLOaICAL CHEMISTRY. i. 89 benzaldehyde is added to a hot concentrated urine which has previously been treated with lead acetate a dark red coloration is produced.On cooling and careful addition of ammonia the colouring matter is precipitated and may be purified by crystal- lization from dilute alcohol. Ten to 12 litres of fresh urine yield 0.02 to 0.06 gram of pure substance m. p. about 220". The spectral behaviour of the substance has been examined and its extinction coefficient used as a measure of purity. Its tinctorial power is very great. The substance is apparently not identical with the colouring matter of Ehrlich's reaction on pathological urine. H. K. Origin and Destiny of Cholesterol in the Animal Organism. XII. The Excretion of Sterols in Man. JOHN ADDYMAN GARDNER and FRANCIS WILLIAM Fox (Proc.Roy. SOC. 1921 [B] 92 358-36'7) .-The present paper revises earlier results (Ellis and Gardncr A. 1913 i 222). It is now shown that in man the amount of sterols excreted in the faeces is in excess of that taken in with the food. The intake however of unsaponifiable matter not precipitated by digitonin (cf. A. 1921 i 639) is larger than the output. It is concluded from the results that the human organism is capable of synthesising cholesterol. Experimental Toxic Haematoporphysia. PIETRO BIKDA (Arch. Farm. sperim. Sci. a#. 1921 31 181-l91).-The results of the author's experiments with rabbits indicate that chronic sulphonal poisoning does not determine elimination of hzmato- porphyrin by the kidneys that animals poisoned by sulphonal keep their power of retaining and elaborating injected hzemato- porphyrin and that in the organs of animals billed by chronic sulphonal poisoning the original property of reducing haemato- porphyrin in vitro is preserved.N. R. BLATHERWICK ( J . Biol. Chern. 1921 49 193-199).-Cases of mild and moderate diabetes can utilise satisfactorily large amounts of fat as indicated by the blood f a t level and the absence of acetone substances from the urine. E. S. T. H. P. Blood Fat in Diabetes. G . B. Lipaemia. W. R. B ~ o o ~ t ( J . Biol. Chern. 1921,49,201-227).- In most cases a sequence in the appearance and disappearance of fat lecithin and cholesterol is perceptible fat being the first to increase and to disappear. I n most cases the ratio lecithin/cholesterol is distinctly below normal its the cholesterol is increased in greater proportion than the lecithin.The increase in fat is generally in still greater proportion. G. B. Action of certain Bismuth Derivatives on Syphilis. R. SAZERAC and C. LEVADITI (Compt. rend. 1921 173 1201- 1204).-It is shown that ammoniacal bismuth citrate bismuth lactate bismuth subgallate and bismuth oxyiodogallate are all active against syphilis but vary in their toxic power. For humani. 90 ABSTRACTS OF CHEMICAL PAPERS. therapeutics sodium or potassium bismuthotartrate are the best bismuth preparations to use. The Action of Polished Metals on Toxins. F. ERDSTEIN and L. FORTH (Biochem. Z. 1921,118,256-258).-A confirmation of Luger and Baumgarten’s results (Wien. klin. Woch. 1912 1222) that copper and to a very slight extent silver have a harmful effect on toxins.An actual destruction of the toxin takes place in the sense that a complex metal-toxin compound is formed. Toxicity of Methyl Alcohol. ASTRID CLEVE VON ErJLER (h’ve?asE. Kem. Tidskr. 1921 33 114-119 ; from Chem. Zentr. 1921 iii 740).-Methyl alcohol is considered by the author to be less poisonous in large doses than ethyl alcohol. Cases of poisoning by methyl alcohol arc to be attributed to accompanying poisonous impurities. G. W. R. The Action of Organic Kations on the Vascular System and its Modification by Inorganic Ions. WERNER TESCHEX- DORF (Biochem. Z . 1921 118 267-285).-The action of a number of salts of strong organic bases was examined on the frog’s vascular system. Acetylcholine had the most powerful constricting action.Nitrosocholine was much less active and guanidine still less so. In the homologous series of quaternary ammonium bases tetra- methylammonium chloride was intermediate between acetylcholine and nitrosocholine the tetraethyl derivative resembled guanidine whilst the tetrapropyl derivative depressed the vascular tonus. The action of the above organic kations was inhibited by the bivalent inorganic kations in the order Mg Ca Sr Ba. Degradation of Fatty Acids in the Animal Organism. P. WORINGER (BUZZ. Xoc. Chim. BioZ. 1921 3,311-450).-A review on much the same lines as Dakin’s monograph. Here and there the author puts forward independent views. Thus he argues against Dakin’s conception of the breakdown of tyrosine and phenylalanine and considers that the fundamental condition necessary for the combustion of an aromatic substance is its capacity of being transformed into homogentisic acid.He thus accepts Abderhalden’s view (A. 1912 ii 585) that this acid is produced in the normal tyrosine metabolism. The title of the review scarcely represents its full scope as it also deals with hydroxy- keto- and amino-acids. A special feature is a tabulation of the transformations of acids hitherto observed in the animal with a statement of the method employed and a literature reference. W. G. 13. K. H. K. There is also a full bibliography. G. B. A New Antianaphylactic Substance Sodium Formalde- hydesulphoxylate. P. BROPIN and P. HUCHET (Compt. rend. 1921 173 865-867; cf. ibid. 1919 168 369; 169 9).-Sodium formaldehydesulphoxylate CH,(OH)*SO,Na can be injected into dogs or rabbits to the extent of 1 gram per kilo. of live weight without any ill-effect and like sodium chloride it has an immunising action against an anaphylactic injection. W. G.VEGETABLE PHYSIOLOGY AND AQRICULTURE. i. 91 The Behaviour of Pyrrole in the Animal Body. TOMIHIDE SHIMIZU (Biochem. Z. 1921 117 26&-268).-Injection of an aqueous suspension of pyrrole into dogs is followed by its elimination in the urine as methylpyridine. H. K. Behaviour of Phrenosine in the Animal Body. TOMIHIDE SHIMIZU (Biochem. Z. 1921 117 263-265) .-Phrenosine ad- ministered to a dog appeared in the urine as sphingosine; the latter when given either by the mouth or subcutaneously to dogs or rabbits appeared unchanged. H. K.

ISSN:0368-1769    

DOI:10.1039/CA9222200079

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 91 Chemistry of Vegetable Physiology an d Ag ri e ul t u r e. The Nature of the Butyric Acid and Butyl Alcohol Fer- mentation. Fixation of Acetaldehyde as a Decomposition Product. Transformation of the Aldol of Pyruvic Acid into Butyric Acid. Production of Higher Fatty Acids from Sugar. CARL NEUBERG and BERNHARD ARINSTEIN (Biochem. Z. 1921,117 269-314) .-Dextrose in a nutrient medium of inorganic materials and in the presence of a fixative for example sodium sulphite is fermented by Bacillus butylicus Fitz with production of about 10% of acetaldehyde. By the use of a culture of Amylobacter acetaldehyde could also be qualitatively recognised. Acetaldehyde or its condensation product aldol is not the intermediate stage in the butyric fermentation but the aldol of pyruvic acid a-keto- 7-valerolactone-7-carboxylic acid which gave butyric acid on fermentation.Starch syrup fermented by a culture of B. butglicus Fitz in an inorganic nutrient medium gave small quantities of t l w higher fatty acids of which decoic was identified. H. K. Action of Aspergillus glaucus on Glycerol. I?. TRAETTA- MOSCA and M. PRETI (G'azxetta 1921 51 ii 269-277).-When Aspergillus glaucus is grown in a nutrient liquid containing glycerol the latter yields the compound C,H,O m. p. 154" previously obtained from sucrose or invert-sugar by the action of the same mould (A. 1914 i 1114). This compound forms a methyl ether C,H,O,*OMe which crystallises in white needles m. p. 165" and unlike the original compound gives no coloration with ferric chloride solution.Hydrolysis of the methyl ether by means of barium or calcium hydroxide results in the formation of methyl- acetol ether and oxalic and formic acids whilst the action of ammonia yields pyridone. The structure of the compound Perataner and Tamburello's maltol (A. 1005 i 807). C,H,O is probably CH<o.C(OH)&*CH,*OH CH-CO .\ and is similar t o T. H. P.i. 92 ABSTRACTS OF CHEMICAL PAPERS. The Longevity of certain Species of Yeast. ARTHUR R. LING and DINSHAW RATTONJI NANJI (Proc. Roy. Soc. 1921 [B] 92 355-357).-Cultures of eight different species of yeast were found to be still alive after thirty-four years’ storage on dry cotton wool pads contained in sealed flasks. Alcoholic Fermentation by means of Heast-cells under Various Conditions. I.Influence of Animal Charcoal and other Adsorbents on the Course of the Fermentation forsch. 1921 5 89-109).-The addition of animal charcoal to a solution containing sugar and yeast -cells effects acceleration of the fermentation and such acceleration appears to be due to the formation of acetaldehyde which is always detectable in the liquid under these conditions. It is uncertain if the acetaldehyde is a product of the degradation of the dextrose or a secondary product formed by oxidation of the ethyl alcohol but it is found that addition of yeast and animal charcoal to aqueous alcohol results after a time in the appearance of an odour of acetaldehyde. Since animal charcoal is an excellent adsorbent for acetaldehyde i t is possible not only that i t takes part in the secondary formation of acetaldehyde from ethyl alcohol but that it concentrates on its surface and thus renders detectable acetaldehyde formed as a primary product of the fermentation of sugar.Alcoholic Fermentation by means of Yeast-cells under Various Conditions. 11. EMIL ABDERHALDEN (Permentforsch. 1921 5 110-1 18 ; cf. preceding abstrac t).-Further investigations show that acetaldehyde solutions which show no loss in weight when left in contact with either animal charcoal or yeast im- mediately begin to evolve gas when both the charcoal and yeast are added. Experiments were made also with pyruvic acid and with methyl and ethyl alcohols it being found that all the samples of animal charcoal tried accelerated the fermentation of sugar by means of yeast caused formation of acetaldehyde and induced formation of acetaldehyde and carbon dioxide from pyruvic acid but that some samples were totally unable to effect transformation of acetaldehyde or alcohols.Functions of the Yeast-cell. Zymase and Carboxylase Action. EMIL ABDERHALDEN and A. FODOR (Ferment forsch. 1921 5 138-163).-The authors consider that the fermentations effected by zymase in its plasma form and by liberated zymase are quantitatively and kinetically different processes and have carried out various experiments with the object of ascertaining how dried yeast differs from the living cell and what substances are removed from living or dried yeast by pressing or maceration. Dried yeast is found to contain cells which in a fermentable solution swell and resume their life functions.Like yeast juice yeast sterilised by treatment with acetone or by age is incapable of fermenting dilute sugar solutions all such preparations lacking the ability to concentrate peculiar to the living cells. Apparently E. S. Formation Of Acetaldehyde. E-MIL ABDERHALDEN (Ferment- T. H. P. T. H. P.VEGETABLE PHYSIOLOGY AND AGRICULTURE i. 93 owing to its simpler and more independent relation to the proto- plasm the carboxylase of dried yeast is able to exert its activity before the whole of tix water necessary for the complete vital functions has been absorbed. The results of various experiments with maceration juice are described these dealing with the kinetics of the fermentation with the persistence both of the fermentative activity and of the carb- oxylase of the juice with the oxygen absorbed by the juice and with kinetic measurements on mixtures containing pyruvic acid dipotassium hydrogen phosphate and maceration juice.The fermentative ability and the power to absorb oxygen fall gradually to zero together. Organic Nitrogen as a Possible Factor in Stimulation of Yeast. WILLIAX D. FLENING ( J . BioZ. @hem. 1921 49 119-122).-The ;,timulation of yeast growth is not due to water-soluble vitamin-B for it persists after the rice extracts have been evaporated wit'h 10% sodium hydroxide to inactivate the vitamin. The stimulation is due to organic nitrogen (cf. Fulmer Nelson and Sherwood .I. 1921 i 292). Comparative Experiments on the Inhibitive Action of some Chlorine Derivatives of Methane Ethane and Ethylene on Fermentation. H.PLAGGE (Biochem. Zeitsch. 1921 118 129-143).-~m-Dichloro- and ap-dichloro-ethane dichloromethane chloroform and tetrachloroethane are toxic to the yeast-cell. The determining factor is not the concentration of t'he solution but the actual dose administered. Fermentation without Yeast. EXIL BAUR and EUGEN HERZFELD (Ijiochem. Z. 1921 117 96-112).-&1ixtures of sub- stances in imitation of yeast press juice (peptone dextrose dextrin sodium hydrogen carbonatc casein lipoid and bile salts) produced carbon dioxide and alcohol (iodoform test) in small amounts The lormation of acid substances from dextrose liberating carbon dioxide from the sodium hydrogen carbonate only accounts for a portion of the gas formed.Behaviour of Diastase and other Enzymes under Ufdavour- able Conditions. Action of some Nitrogenous Compounds on Germination. TH. BOEORNY (Bied. Zentr. 1921 50 429- 430).-Brief reference is made to the effect of acids bases salts of heavy metals etc. on such enzymes as diastase invertase pepsin myrosin and trypsin. From an examination of the effect of urea hippuric acid am- monium salts and sodium nitratc on germination it is shown that nutrient materials are injurious if used a t too high a concentration. D. H. WESTER (Biochem. Z. 1921 118 168-163).-The manganese content of the seeds of 48 species of plants was determined the quantity of T. H. P. Vitamine Content of Rice by the Yeast Method. G. B. H. I<. H. K. W. G . The Manganese Content of (Dutch) Seeds.i.94 ABSTRACTS OF CHEMICAL PAPERS. metal generally present being between 2 and 6 mg. in 100 grams of dried material. H. K. Is it Possible to Determine the Value of Seeds by a Bio- chemical Method? ANTOIKE N ~ E C and FRANQOIS DUCHO~ (Compt. rend. 1921 173 933-935).-The activity of the various hydrolysing enzymes such as amylase invertase glycerophos- phatase lipase urease uricase and phytopsoteases of seeds dimin- ishes with the germination capacity of the seeds but is still marked when the latter has reached zero. Catalase is different and there is some indication that the activity of the catalase measured under comparable conditions may represent a suitable means for determin- ing rapidly and simply the agricultural value of seeds. E. CHEMIN (Compt. rend.1921 173 1014-1016).-Further experiments are given in support of the view that plant roots do not excrete any sensible amount of acids other than carbonic acid and that the excretion of the latter is sufficient to explain the corrosion of marble. W. G. Corrosive Action of Roots on Marble. W. G . The Part Played by Lipoids in the Metabolism of Plant Cells. FRIEDRICH BOAS (Biochem. Z. 1921 117 166-214).- The influence of saponin and salts was investigated on the growth of yeast and the course of fermentation. The action of these agents is similar to their known action on animal cells the com- bined action leading to destruction of the cell. The anions and kations of the salts influence the colloidal state of the cell wall and follow the lyotrope series. The Effect of Neutral Salts on the Heat Coagulation of Plant Protoplasm.HUGO KAZRO (Biochem. Z. 1921 11'7 87-95).-Both ions of neutral salts play a part in the heat coagula- tion of the protoplasm of the epidermal cells of Trade.scuntia xebrina. The coagulation is accelerated by anions arranged in the lyotropic series. Neutral salts which penetrate the plasma membranes most readily have the greatest lowering effect on the temperature of coagulation. H. K. The Relation between Fluorescent Substances which Act in the bark and their Photodynamic Activity on Cells. A. JODLBAUER and F. HAFFNER (Biochem. Z. 1921 118 150- 157) .-A large number of fluorescent and non-fluorescent substances of known photodynamic action on cells (for example paramoecia) have been examined in respect of their action in the dark on the hzemolysis of erythrocytes a t room temperature and a t 56" and in the flocculating property on the colloidal contents of hzmolysed corpuscles a t 56".In general there is a parallelism between the two actions. H. K. Rhythmic Precipitation Phenomena in Cell Membranes of Plants. HANS PETER MOLLER (Kolloid Chem. Beihefte 1021 14 97-146).-When wheat grains which have been cut are treated with a solution of silver nitrate bands and layers are formed a t H. K.VEGETABLE PHYSIOLOGY AND AGRICWLTVRE. i. 95 right angles to the direction of diffusion in the membranes of the aleurone cells and in the nucellus layer which are identical with the zones discovered by Liesegang in artificial colloids. The identity between the rhythmic precipitation in plant cells and Liesegang’s rings and zones is proved (1) by the form and appear- ance of the bands and (2) by the fact that the effect of external agencies is the same in both cases.In both cases the rhythmic precipitation of silver nitrate occurs after a region of formless preci- pitate ; zones are produced which increase in width and distance apart with increasing distance from the centre of diffusion. With increas- ing width the formation of grains occurs and the edges of the zones become indistinct the space between the zones becomes tlurbid and finally the rhytlimic zone formation passes over into an irregular granular precipitate. Fick’s law of diffusion is approxi- mately applicable to the diffusion of silver nitrate in wheat grains the water content of the membrane its content on silver nitrate and the concentration of silver nitrate have the same influence as in the diffusion into jellies.The formation of a rhythmic pre- cipitation depends on the velocity of diffusion of silver nitrate. The zone formation commences so much nearer to the centre of diffusion the smaller the concentration of silver nitrate and the lower the temperature. The velocity of invasion of the silver is of equal importance which apart from the concentration of silver nitrate is influenced by the content of the cell walls on silver pre- cipitating salts and wa,tor. In wheat grains a larger and smaller rhythm cannot be detected. The dinensions of the width and distance between the bands are the same for plant cells which have had a previous treatment with silver nitrate and those which have not been so treated.The grains of other cereals and the leaves of many plants show a similar zone formation when treated with silver nitrate so that it may be assumed that the cellulose membranes of plants in general are capable of showing rhythmic precipitation when the necessary external conditions are obtained. From the experiments it follows that the pure cellulose membranes of the wheat grain which show rhythmic precipitation cannot be regarded as a selective permeable layer and it further follows that the woody integument layer of the sheath of the wheat grain is the selective permeable i~ernbranc. The Distribution of Manganese in the Organism of Higher Plants. GABRIEL BERTRAND and (MATE) M.ROSENBLATT (Compt. rend. 1921 173 1118-1120).-From a study of the dis- tribution of manganese in the different parts of a dicotyledon Nicotiana rustica L. and of a monocotyledon Lilium lancefolium rubrum it is shown that those organs in which chemical changes are the most intense contain the highest percentages of manganese. The seeds contain a high proportion of manganese doubtless for the use of the future seedling. Lumbang Oil (Candlenut Oil). AUGUSTUS P. WEST and ZOILA MONTES (PhiZippine J . Sci. 1921 18 619-636).-The oil is obtained from the nuts of Aleurites molucmnu and has the following J. F. S. W. G.i. 96 ABSTRACTS OF CHEMICAL PAPEBS. composition glyceryl linolenate 6.5y0 glyceryl linolate 33*4y0 glyceryl oleate 56.9y0 glycerides of solid acids 2.8%.It is insoluble in cold ethyl and methyl alcohols and acetic acid. The oil behaves in much the same manner as linseed oil on oxidation. It is an excellent drying oil. 3'. E. POWER and V. K. CHESNUT (J. Amer. Chem. Soc. 1921 43 1741; cf. A. 1920 i 653).-Inasmuch as esters derived from leucic acid do not occur in apples (Zoc. cit.) the title of a paper by Kodams on this subject Characteristics and Utilisation of Beech Nut Oil. H. B. (Mat. grasses 1921 13 5860-5881).-The oil contenh of beech nuts varies from 14 to 2274. The constants of Ghe oil are d15 0.9205 iodine number 104.4 bromine number 0.652 heat developed with sul- phuric acid + 65" polariscope reading -0.8" in saccharimeter degrees refractometer reading +I605 to 3-1s". The oil is edible and may be kept without change for a long time.The cake from the nuts gave the following analysis decorticated cake water 1 2 . 5 ~ o O i l 7*5y0 nitrogenous matter 37.1 yo non-nitrogenous extract 29.7% cellulose 5.5yo ash 7.7% ; non-decorticated cake water 19.1 yo oil 8'34y0 nitrogenous matter 1S*15yo non-nitrogenous extract 28.39Y0 cellulose 21)-89 yo ash 5-13 yo. The non-decorticated cake is poisonous. CHEMICAL ABSTRACTS. JEAN RIPERT (Compt. rend. 1921 173 928-930).-Belladonna plants grown in obscurity show an increase in alkaloid content both in the leaves and in the stems whilst the amount in the roots diminishes very slightly. When the plants are returned to sunlight the values €or the leaves return to a practically normal figure after thirteen days. The protein content of the leaves also increases considerably when the plants are kept in the dark.F. M. ANDREWS (Proc. Ind. Scad. Sci. 1917 167).-The anthocyanin of B. vulgaris affords one of the examples where the pigment forms in the subterranean parts. A st'rong solution of such anthocyanin mill preserve its normal colour in it test-tube placed in darkness for more than a week. In direct sunlight it will retain its normal bright colour for a week or more until disorganised by bacterial action which change finally occurs in tthe anthocyanin solution in the dark. H. C. R. The Odorous Constituents of Apples. (cf. A. 1921 i 220) is misleading. w. G. The Biology of the Alkaloids of Belladonna. W. G. Anthocyanin of Beta wzdgaris. CHEMICAL ABSTRACTS. Formation of the Wed Pigment of Beta vulgaris by Oxida- tion of the Chromogens.ANTOINE KOZLOWSKI (Compt. rend. 1921 173 855-8~7).-Details are given for the extraction of the chromogens from beetroot by alcohol and for their subsequent purification and isolation. The chromogens extracted from the white sugar- beet resemble saponins in certain of their physico- chemical properties and on oxidation give 8 coloured pigmentVEGETABLE PHYSIOLOGY AND ABRI-TTURE. i. 97 having the same spectroscopic characteristics as the red pigment extracted from red beetroots and showing similar colour changes with acids and alkalis. Transformation by Oxidation of the Chromogens of some Plants into a Red Pigment. ST. JONESCO (Compt. rend. 1921 173 1006-1009).-The yellow chromogens extracted from such plants as Cobcea scandens and Ampclopsis hederacea on oxida- tion in amyl alcoholic solution with sulphuric acid and manganese dioxide a t 50-60" give a violet-red pigment.I n the case of the chromogens from Ampelopsis reduction was tried but red pigments were not obtained. The results obtained confirm those of Koz- lowski on beetroot pigments (preceding abstract) that the appear- ance of red pigments in plants is due to oxidation and not to reduction phenomena. W. G. Formation of Anthocyanin in the Flowers of Cobcea scandens at the Expense of Pre-existing Glucosides. ST. JONESCO (Compt. rend. 1921 173 850-852).-Contrary to the results of Rose (A. 1914 i 639) experimental evidence is given to show that the anthocyanin glucosides in the flowers of CobcFa scandens are formed a t the expense of pre-existing glucosides and consequently Combes's hypothesis as to the formation of antho- cyanin (cf.A. 1909 ii 426) is incorrect. The Effect of Daylight on the Content of Active Material in Digitalis. OTTO VON DAFERT ( B i d Zentr. 1921 50 422- 425).-The toxicity of the extract from Digitalis leaves depends on the time of day a t which the leaves are gathered and how and when the leaves are killed. To obtain the most toxic extract the leaves should be gathered in the afternoon and immediately The Occurrence of Methyl Anthranilate in Grape Juice. FREDERICK B. POWER and VICTOR K. CHESNUT ( J . Amer. Chem. Soc. 1921 43 1741-P742).-Methyl anthranilate is a natural and apparently constant constituent of grape juice. Its presence therefore in a commercial grape juice must not necessarily be taken as an indication of adulteration. Grape Oil from the Canadian Vine (Vitis hederacea).(Boll. CLSSOC. ital. piante med. aromat. 2 56-59; Bull. Agr. Intelli- gence 1919 10 1004-1005).-Two oils were extracted (1) from the pips a dark yellow or green oil with sweet taste and nutty odour d15 0.9215 n15 1.4778 saponification number 189.2-189.6 iodine number 131-4-141-6 fixed fatty acids 93-97y0 volatile fatty acids O% and non-saponifiable substances 1.44y0. The total fat%y acids have iodine number 144.6 and mean molecular weight 281.2. Solid fatty acids consisting chiefly of palmitic acid do not exceed 3y0 have a mean molecular weight of 261-4 and m. p. 57.6". The liquid fatty acids are chiefly oleic and linoleic acids with iodine number 14843-149.9; (2) from the pulp and skin an olive-green soft pasty oil with astringent taste and pleasant odour turning rancid in the air n15 1.4722 saponification number 192.3-193.3 iodine W.G. W. G. killed by plunging them into 96% alcohol. w. G . W. G.i. 98 ABSTRACTS OF CHEMICAL PAPERS number 90.3 fixed fatty acids gay0 volatile fatty acids O% and unsaponifiable substances 1.67%. The total fatty acids have iodine number 94.4-94.6 and mean molecular weight 278.8. The solid fatty acids are about 10% of the pulp and skin oil chiefly palmitic acid. The liquid fatty acids are mostly oleic and linoleic acids with iodine number 1 10.2. Oil from the Seeds of Jatrophu Curms L. CLEMENS GRInlMe (Seifenfabr. 1921 41 513-515 ; from C'hem. Zentr.1921 iii 1035).-The seeds of Jatropha Curcas L . consist of 38% hard husk and 62% oil-bearing kernel. Analyses of the seeds are given. Fn spite of the high protlein content 48.13% thc seeds are unsuitable for use as a feeding stuff on account of the presence of highly poisonous curcine. A complete description is given with constants of the oil obtained by extraction hot pressure and cold pressure respectively. The principal constants are d15 0.9213- 0.9228; m. p. 5-8"; 12:; 1.4610-1-4618; acid number 3-18- 4.05; iodine number (Wijs) 96*7-98.8. The fatty acids are white to yellow in colour and have m. p. 15-18'. The oil helongs to the class of non-drying oils and consists of the glycerides of palmitic myristic and curm?zoZic acids. The latter is a hydroxy-acid like ricinolic acid. The seeds contain a lipolytic enzyme which how- ever is not so energetic as the enzyme in Ricinus seeds.CHEMICAL ABSTRACTS. G. W. R. Iodine in the Lamitauria. P. FREUNDLER (MLLE) Y. MENAGER and (MLLE) Y. LAURENT (Compt. rend. 1921 173 931-932).- An examination of the iodine content of certain species of Laminaria shows that they lose a certain amount of iodine during drying the loss amounting in some cases t o as much as 50%. The iodine content is dependent on the time of harvesting being higher in July than in March. It is independent of the place of growth but varies with the age of the tissues being highest in the youngest tissues. The variations with different parts of the plant are not uniform but differ with the species. P. FREUNDLER (MLLE) Y.MENAGER and (MLLE) Y. LAURENT (C'oinpt. rend. 1921 173 Z 116-1 118 ; cf. preceding abstract).-The authors have correlated the variation in iodine content of the Laminaria with their bio- logical evolution and show that the maxima for iodine content as well as for the percentages of reserve carbohydrates and brown pigments coincide with the period of maximum sunshine. The Laminaria regularly restore to the sea it certain amount of their iodine under conditions which depend for each species on their mode of growth. W. G. YOSHITORA IWAMOTO ( J . Chem. Ind. Japan 1921 24 1143-1160).-A yellow- ish-brown oil is obtained by pressure or extraction of the seed of " Tohaku," Lindera obstiroba B. L. which is widely diffused in Corea. Its physical and chemical constants were determined.Decoic lauric and oleic acids and an acid C12H2P02 which occurs W. G. The Composition of the Laminaria. Properties and Composition of Tohaku Oil.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 99 in cochineal fat were identified. Some of the lower unsaturated liquid and solid fatty acids seem to be present but linolic linolenic stearic and palmitic acids are probably absent. K. K. The Proteins of the Alfalfa Plant Fucerne]. THOMAS B. OSBORNE ALFRED J. WAKEMAN and CHARLES S. LEAVENWORTH ( J . Biol. Chem. 1921 49 63-91).-The paper is mainly concerned with a technique for extracting plant proteins with as little change as possible. Fresh plants or plants frozen soon after cutting are ground very finely and pressed in a hydraulic press ; the undiluted juice contains 10% of solids.The addition of 20% of alcohol precipitates a colloid consisting of 70% of protein and calcium salts. The latter are extracted by dilute alcoholic hydrochloric acid which forms an insoluble hydrochloride of the protein. The latter is further purified by heating with dilute alkali hydroxide and reprecipitation. By successive extraction with water alcohol dilute aqueous alkali and hot alkaline alcohol practically all the cell contents can be extracted if the fresh plant is sufficiently thoroughly ground. Thirty-two per cent. of the solids of the plant containing only 56% of its nitrogen finally remains undissolved. The Odorous Constituents of Peaches. FREDERICK B. POWER and VICTOR K. CHESNUT (J. Arner. Chem. Xoc. 1921 43 1725-1739) .-An examination of the pulp of choice ripe peaches shows that the odorous constituents of the fruit consist chiefly of the linalyl esters of formic acetic valeric and octoic acids together with a considerable proportion of acetaldehyde and a very small amount of an aldehyde of higher molecular weight.It is probable that the volatile acids are present to some extent in a free state. No trace of hydrocyanic acid or benzaldehyde could be detected in the distillabe from peach pulp. The yield of essential oil was about 0*000’74~0 of the fresh pulp aqd the oil contained in addition to the linalyl esters a little acetaldehyde and furfuraldehyde probably some cadinene and a very small amount of an unidentified paraffin hydrocarbon. The essential oil is very unstable and on exposure to air for any length of time is converted into a black viscid mass and loses its original fragrance.The emanation from the entire ripe fruit contains a minute amount of acetaldehyde. W. G. Constituents of Phellodendron Amurense. K ~ T A R ~ S m o (Sci. Rep. Tohoku Imp. Univ. 1921 10 331-338).-The rind of Phellodendron Amurense contains berberine and fatty acids. These acids appear to exist uncombined with berberine and consist of palmitic acid linoleic acid and a small quantity of linolenic acid. A small quantity of a neutral substance was found in addition but was not identified. Two samples of phellodendron rind gave 2.473 Yo and 3.75% respectively of berberine (estimated as berberine acetone). G. W. R. The Cellulose Content of Pine Wood. PETER KLASON (Zelktoflchem.Abi”landlungen 1921 1 No. 5 105-114).-~oss and Bevan’s method cannot be used for the estimation of the cellulose G. B.i. 100 ABSTRACTS OF CHEMICAL PAPERS. content of pine wood. The author has investigated the action of a solution of 80 grams of sodium hydrogen sulphite and 500 C.C. of N-hydrochloric acid in one litre of water for varying periods of time at looo. After eight days the cellulose reaches a nearly constant value and with continued heating only slowly decreases (1.7% in 13 days). He finds 53% of cellulose in pine wood. The composition of woods of various ages is also investigated. CHEMICAL ABSTRACTS. Chemical Constituents of Pine Leaves. 11. ASTRID CLEVE VON EULER (Tekn. Tidsk. Kern. Berg. 1921 51 35-38 47-52).- A study of the non-fatty impurities insoluble in ethyl ether present in the crude fat of pine leaves.The material is more conveniently extracted by means of 93% methyl alcohol and is designated “crude gum.’’ It readily changes into an insoluble substance the change being facilitated by the presence of acids. A solution of the gum in sodium hydroxide showed marked changes when treated with carbon dioxide. Fractional precipitation of the alkaline solution of the gum with acids yielded coniferyl alcohol and dihydroxy-7-phenylpropyl alcohol ; the whole crude gum is tannin-like in character and is considered to consist of inter- mediates in the plant synthesis of tannins. CHEMICAL ABSTRACTS. The Organic Acids of Pyrus coronaria L. Rhus glabra L. and Acer saccharurn Marsh. CHARLES E.SANDO and H. H. BARTLETT ( J . Agric. Research 1921 22 221-229).-The organic acids of the wild American crab apple Pyrus coronaria L. smooth sumac Rhus glabra L. and sugar maple h e r saccharurn Marsh were investigated. In all cases the acid found was malic acid occurring in the form of the free acid in the first species the acid calcium salt in the second species and both acid and normal calcium salts in the third species. A pertain amount of gallic acid is also found in the second species. The substance known as “maple sand ” obtained in the preparation of sugar from the sugar maple is crude calcium malate. It appears that succinic acid may be formed autolytically from the malic acid of Pyrus coronaria. G. W. R. Volatile Substances from the Bark of Rhamnus frangula. 0. A. OESTEBLE (Schweix. ApotR.-Zeit. 1921 59 341-345 ; from Chem. Zentr. 1921 iii 73&-735).-By steam distillation of the bark of Rhamnus franguka 0.05-0.1 yo was obtained of a substance of unpleasant odour which contained in addition to dark coloured impurities a white substance insoluble in sodium carbonate crystallising from chloroform-light petroleum in long needles a compound obtained as a gelatinous precipitate from hot sodium hydroxide solution a substance crystallising from hot water in slender ray-like aggregates and a main portion consisting of brownish-yellow platelets with a green tinge crystallising from &lute ethyl alcohol The latter substance is tasteless and odourless and has the empirical formula C,,H,,Og It is easily soluble in organic solvents and has m. p. 100-101 . G. W. R.

ISSN:0368-1769    

DOI:10.1039/CA9222200091

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 97 General and Physieal Chemistry. Refraction of Light at Corresponding Temperatures W. HERZ (2. p,kysikaE. Chem. 1921 98 175-180).-A theoretical paper in which from the examination of the data for a large number of substances it is shown that the refractive index of all substances has the same value 1.126 a t the critical temperature. The formulze of Gladstone and Dale and of Lorentz and Loreilz yield approxi- mately the same specific refraction values for this temperature. It is also shown that at other comparable temperatures the refrac- five indices approximate to the same value although in these cases considerable differences do occur. Thus a t the boiling point ten liquid substances give mean value of 1.335 for the refractive index the extreme values being 1.348 and 1.320.The Spectrochemistry of Aliphatic Dienes with Conjugated Double Bonds. K. VON AUWERS and H. WESTERMANN (Ber. 1921 54 [B] 2993-2999).-The physical constants of a number of carbinols and the corresponding dienes are recorded. The specific exaltations in the cases of the latter substances with " un- disturbed doubly disturbed and singly disturbed " conjugation are E&fr. +2.0 +1.4 and +0.9 andE8Dbp. +50% +43% and -+%yo respectively. The boiling points of the &enes are de- pressed by branching of the chain but raised by the approximation of the methyl group to the double bond; this regularity is not always very definitely marked. The density of isomeric com- pounds increases relatively greatly when the methyl group is attached to a doubly-bound carbon atom.Similarly the index of refraction increases with similar alteration in structure ; these changes are consonant with those observed with cyclic compounds. The following constants are recorded As-pentene-8-01 b. p. 64"/62 mm. d:795 043382 ni795 1.42558 ngy5 1-42821 nFQ5 1.43502 72"':15 1.44065. As-Hexen-8-01 b. p. 59"/27 mm. djJJ 0.8370 n?j 1043025 nE3 1.43286 n r s 1.43962 n,;' 1,44510. Ab-Heptene-8-01 b. p. 63"/11 mm. d:" 0.8422 n:4 1.43698 nE'4 1.43965 nF4 1.44620 nY.4 1.45176. c-Methyl-Ab-hexen-8-01 b. p. 75"/45 mm. dig 0.8411 nz 1.43539 n$ 1.43788 ng 1-44478 n y 1.45045. [-Methyl-As- hepten-8-01 b. p. 67"/11 mm. dY2 0.8354 nyd 1-43679 nEd 1.43926 nlS2 1.44585 ny2 1.45127. y-Methyl-Afi-octen-&ol b. p. 85"/12 lnn~. d:4'5 0.8402 n:' 144202 ng5 1.44448 nF5 1.45114 nId5 1.45651.&Methyl-Ay-heptene-c-ol b. p. 66"/17 min. dli 0.8525 i L 7 9 1.44525 n::9 144792 nF9 1.45454 nyy 1.46018. 6-Methyl-A~-octen-~-oI b. p. 89"/16 mm. d y 5 0.8495 n:' 1.44576 ng5 1.44838 nF5 1.45490 ny'B 1.46059. A@-Pentadiene b. p. 43" d:"''j 0.6887 di;6 0-685 n26 1.42991 ?g~ 143M3 nFS5 1.44655 "Rt;"j 1.45694 nz!j' 14309. Afi8-Hexadiene b. p. J. F. S. Y B VOL. UXXII. ii. 4ii. 98 ABSTRACTS O F CHEMICAL PAPERS. 80" d:"' 0.7237 d;,7O5 0.720 n;'O5 1.44962 n:'O5 1.45420 n;'O5 1.46651 n;'O5 1.47764 n'," 1.4514. A@-Heptadiene b. p. 107" d.i6'; 0.7341 dit.3 0.731 nz"3 1-45101 n;'' 1.45543 ng'3 1.46695 n;"" 1.47735 1.4534. [-Methyl-A@-heptadiene b. p. 117",d~5'50~7361,d~~'50~733,n~'~ 1.44887 n:.' 1.45302 nF'5 1.46397 ny'5 1-47379 n$ 1.4505.Y-Mefhyl-AflS- octadiene b. p. 149" 0.7515 dii'6 0.751 145427 nS.6 T.45831 nF-6 1.46903 n:'6 1.47812 7~: 1,4553. c-Methyl-Afls-hexadiene b. p. 104" dt:'7 0.745 n 1.4606 (i) dig'' 0.7439 7~:'~ 1.45659 n',"'' 1.46117 nF'7 1.47340 n;:'i 1.48433 (ii) 0.7473 n:'65 1,45589 72g6 1.46037 n;' 1.47262 ny'Os 1.4831 6. P-Methyl-Aay-butadiene b. p. 34" dig'* 0.6826 dii'8 0.682 n:'* 1.41902 n;'* 1.42309 nF's 1.43422 ny'* 1.44405 72; 1.4224. 6-Methyl-Aye-heptadiene b. p. 131" d";"4 0.7598 dii'-? 0.763 n24'4 1.45610 n$'4 1.46003 nFy 1.47125 ny'4 1.48103 n?, 1.4625. 8-kethyl-AyE-octadiene b. p. 150" die" 0.7708 d;;''" 0.771 nz,0'3 1.46206 n::.'" 1.46617 d:"" 1.47724 n20'3 1.48708 n$ 1-4663. py-Dimethyl- Av-butmdiene h. p. 70° d$ 0.7239 d;f" 0.725 nz'l 1.43307 ng'l 1.43703 ny'l 1.44758 n7.l 1.45704 n$ 1.4382.K. VON AUWERS (Ber. 1921 54 [B] 3000-3003).-A reply to K. H. Meyer (A. 1921 i 853). The view that the methyl group causes optical exaltation cannot be mainta,ined. In certain of the examples quoted by Meyer the differences lie within the limits of experimental error whereas in ot,her examples readily polymerised substances for instance acrylic acid and its esters have been chosen and the data obtained are not due to the unimolecular forms. The Molecular Refraction of Aromatic Hydrocarbons and '' Aromatic " Carbon. K. VON AUWERS (Ber. 1921 54 [B] 3188-3194).-1n a recent communication (A. 1921 ii 473) von Steiger has endeavoured to show that the molecular refraction of hydrocarbons can be calculated more accurately from linking refractions than from atomic refractions and he has postulated that all C-C bonds and all C-H bonds in aromatic hydrocarbons are equivalent among themselves but different from the corre- sponding values in the aliphatic series.This mode of calculation appears to the author to be unsound theoretically since the atomic refraction of aromatic hydrogen as deduced from the molecular refraction of benzene diphenyl and naphthalene in these circum- stances is negative whilst also the " linking refraction " for (C-H) falls with decreasing wave-lengths. V O ~ Steiger has illustrated his arguments by citing the cases of benzene diphenyl and naphthalene and the agreement between the observed and calculated values is excellent. Unfortunately the data quot,ed for naphthalene are incorrect and the amended figures show that the presumption of additivity is not fulfilled.Further the data for the three hydrocarbons are not directly comparable since they are obtained under widely-diff ering conditions ; when due allow- ance is made for this factor it is found to be impossible to deduce constant atomic or linking refractions. The molecular refractions H. W. [Substitution Processes]. H. W.GENERA4L AND PHYSICAL CHEMISTRY. ii. 99 of homologues of benzene and other aromatic hydrocarbolls cannot be calculated from von Steiger’s aromatic and aliphatic linlcing refractions since the differences between the observed and calcu- lated values increase more and more with increase in the number of side-chains. The fundamental idea in voii Steiger’s refractometric hypothesis and thermochemical theories (A.1920 ii 355) is the existence of a practically tervalent “ aromatic ” carbon atom of the graphite type which differs from the quadrivalent “ diamond ” carbon atom of the paraffins (cf. Debye and Schemer A. 1917 ii 437). To the author this view of the varying valency appears to be mis- leading. The supposed ter- and quadri-valency of the carbon atom does not as in the case of other elements correspond with different stages of oxidation or different electric charges ; the atom is invariably quadrivalent and the apparent variation is caused by alteration in t’he distribution or compensation of its affinity. H. W. The Mechanism of Continuous Luminous Radiation. J. J ~ C L A U X (Compt. rend. 1921 173 1355-1357).-The author has previously put forward the hypothesis (cf.ibid. 1914 158 1879) that the emission and absorption of the continuous spectrum depend on the establishment or rupture of chemical valencies. Evidence in support of this hypothesis is now given. WILLIAM R. SXYTHE (Astrophys. J . 1921 54 133-139).-Wjfh a discharge passing between gold electrodes the ultra-violet region of the fluorine spectrum was photographed through a fluorite window the gas having been prepared by the electrolysis of potassium hydrogen fluoride and purified by being passed through sodium fluoride and a freezing trap. Ten fluorine lines all in the red were observed arid tabulated with an accuracy of A0.l A. An impurity which was supposed to have the composition CF was observed following a ff are back from the charcoal chamber.The approximate positions of nine heads of bands between A 4829 and A 6525 were observed in this spectrum. ARTHUE ST. C. DUNSTAN and BENJA- MIN A. WOOTEN (Astrophys. J . 1921 54 65-75).-The spectra of strontium barium lithium copper and lead were observed when the vapours of the metals were introduced into a direct current arc by means of an alternating current arc placed below it in the same enclosure. It was shown that by cooling the elec- trodes alternately the intensity of the metallic iines remained as before greater a t the cathode than at the anode when the metal was introduced into the arc symmetrically; neither was the effect due to electrolytic or electrostatic separation. Since the pheno- menon is fully developed in 1/120 second the transference of vapour from one electrode to the other must be of little importance.The light appears to be due chiefly to bombardment of the metallic vapour by electrons from the cathode. Whilst the lines of all W. G. The Spectrum of Fluorine. CHEMICAL ABSTRACTS. Arc-cathode Spectra. 4-2ii. 100 ABSTRACTS OF CHEMICAL PAPERS. metals are stronger a t the cathode the difference decreases with increasing atomic weight. CHEMICAL ABSTRACTS. The Electric Furnace Spectrum of Scandium. ARTHUR S. KING (Astrophys. J. 1921 54 28-44).-The spectrum of a pure sample of scandium oxide was observed in the carbon arc and in the electric furnace through the range A 3015-6559 A. The furnace was operated a t the usual low gas pressure and tem- peratures of 2200° 2250° and 2600" were used.A table gives the classification of 257 lines with respect to their behaviour in the arc and a t various furnace temperatures. Some 25 lines are indicated as being enhanced in the arc; 160 are enhanced in the furnace. The 29 arc-flame lines belong to the latter class some of them showing moderate strength a t all temperatures whilst others increase in intensity more or less rapidly with increasing temperature. These lines are not due to oxidation but the bands on the other hand are quite probably due to the oxide. Lines which appear a t a low temperature and those enhanced in the furnace are weak or lacking in the general solar spectrum but prominent in that of sun-spots. The Zeeman effect for scandium lines is large and apparently uniform in sunspot spectra although laboratory observations have not as yet been made.Scandium oxide fused in the furnace seemed to form a carbide with the graphite of the boat. The glossy black residue became a greyish- brown powder on exposure to the air presumably reabsorbing oxygen. CHEMICAL ABSTRACTS. Wave-length Measurements in Arc Spectra Photographed in the Yellow Red and Infra-red. F. M. WALTERS jun. (Bureau of Standards Sci. Papers 1921 17 No. 411 161-177).- Observations were made with a grating spectrograph of 640 cm. radius and 299 lines' per mm. The photographic plates were sensitised to yellow red or infra-red light with pinacyanol and dicyanin. The wave-lengths of silver aluminium gold bismuth cadmium mercury lead antimony tin and zinc are given in international units and to 0.01 A.The longest wave-length measured is that at 10395 8. in the spectrum of cadmium. The work is compared with previous results of others and discrepancies are accounted for as arising from impurities ghosts or overlapping spectra of higher orders. Extension of the Ultra-violet Spectrum and the Progres- sion with Atomic Number of the Spectra of Light Elements. R. A. MILLIKAN (Proc. Nut. Acad. Xci. 1921 7 289-294).-The results of an investigation of the extreme ultra-violet radiations emitted by the second ring or shell of electrons in the atoms of atomic number 2 to 13 (helium to aluminium) are recorded. The ultra-violet spectrum has been photographed down to 1=136*6 A. in the case of aluminium and to h=149.5 A. in the case of copper.The La lines of aluminium magnesium and sodium are found a t 144.3 b. 232.2 8. and 372.2 b. respectively. Aluminium emits no radia- tions when excited by condensed sparks in a vaeuum between CHEMICAL ABSTRACTS.ii. 101 144.3 8. and 1200 A. where the JI spectrum due to the three outer electrons begins. The chief lines below 2000 8. due to the three outer electrons of aluminium are 1379.7 1384.5 1606.9 1612.0 1671.0 1854.7 and 1862.7 8. Magnesium is like aluminium there is a blank between its La line a t 232.2 8. and the lines due to the two outer electrons which begin a t 1700 8. The lines measured below 2000 A. are 1735-2 1737.9 1751.0 and 1753.7 A. Sodium edits no lines between the L line 376.5 8. and the lines due to the single M electron which have their convergence wave-length a t 2412.63 8.The spectrum due to the six L ring electrons of oxygen begins a t 230 A. and extends with much complexity and strength up to 834.0 8. where the strongest line is found; above this point the lines are few in number and relatively faint. The ratio of the K / L frequency for oxygen is about 35. The strongest oxygen lines are 321.2 374.3 507.8 525.7 554.2 599.6 610.1 616.7 625.2 629-6 644.0 703.1 718.5 and 834.0 8. The spectrum of the four L-ring electrons of carbon begins a t 360.5 8. and extends with much complexity and strength up to 1335.0 8. where the strongest line lies; above this point the lines are widely scattered and rela- tively weak. The ratio of the K / L frequency in carbon is about 30. The spectrum due to the five L-ring electrons of nitrogen is simple; it begins a t 685.6 8.and reaches a maximum at 1085.3 8. The only other strong lines of nitrogen are 685.6 8. 916.2 a. and 991.1 8. The ratio of the K/L frequency is 34-8. In the case of fluorine a strong line appears a t 657.2 A. and a second a t 607.2 A. ; these are the only lines thus far identified as coming from the seven L-ring electrons of fluorine. The spectrum from the three L-ring electrons of boron is very simple. It consists of 676.8 760.0 1624.4 two doublets 2164.2 2166.2 and 2496.9 2497.8 and a single spark line 3451.5 A. The ratio of the frequency K/L is 37. The spectrum of the two L-ring electrons of glucinum begins a t 2175 8. and finishes in its La doublet at 3130.6 and 3131.2 A. Similar experiments with lithium reveal no lines between the shortest wave-lengths measurable by the present method and the familiar series due to its single L-ring electron the Laline of which is a t 6708 pi.and its convergence mave-length a t 2209 A. The progression shown in these optical spectra is simple and very like t,hat exhibited by X-ray spectra J. I?. S. GENERAL AND PHYSICAL CHEMISTRY. The Structure of tho Elements of Mean Atomic Number. A. DAUVILLIER (Conapt. rend. 1921 173 1458-1461).-An exten- sion of previous work (cf. A 1921 ii 669) further results being given for gold and new measurements of the L series for cerium The Structure of the Bismutli Lines. €1. NAGAOKA and Y. SUGIURA (Astrophys. J. 1931,53,339-348).-The light resulting from the bombarding of bismuth by an electronic current was observed by means of a glass Lummer-Gehrcke plate crossed with one of quartz or crossed with an echelon grating.For the line A 4722 the five known positive components were confirmed and and antimony. FV. c.ii. 102 ABSTRACTS OF CHEMICAL PAPERS. seven weak negative satellites were discovered showing the line to have the general structure common to lines of heavy metals. The principal component is probably multiple its constituents varying in relative intensity. The line A 4122 has four strong components. The line A 4308 consists of two principal lines separated by 0.350 A. each being a narrow doublet; there are also two faint satellites. The authors point out some constant frequency differences and suggest that these may be interpreted in terms of the quantum theory.The Zeeman Effect. H. R. WOLTJER (Chem. Weekblad 1921 18 677-682).-A paper written in connexion with the twenty-fifth anniversary (October 31st 1921) of the first announce- ment of Zeeman’s discovery. The importance and subsequent developments of his work are discussed a t some length. Anisotropy of Molecules. C. V. RAMAN (Nature 1922 109 75-76) .-An extension to direct visual observations is described of the method whereby it has been shown photographically (Lord Rayleigh A. 1920 ii 574) that the light scattered by molecules is in general not completely polarised when observed in a direction transverse to the pencil of light traversing the gas. With carbon dioxide the effect is conspicuous and visual determinations of its magnitude have been made.Similar evidence that the molecules of gases are not spherically symmetrical and are anisotropic in their properties is furnished by observations on the polarisation of light of the sky; liquids also show an imperfect polarisation attributable to aniwotropy. H. ZOCHER (2. physikaZ. Chem. 1921 98 293-337).-The double refraction discovered by Diesselhorst Freundlich and Leonhardt (A. 1916 ii 65) with flowing vanadium pentoxide sols has been found in the following sols Soap solution clay suspensions sols of silver cyanate benzo- purpurin “ benzo-brown,” primulin sodium alizarinsulphonate alizarin p-azoxyphenetole p-azoxyanisole anthracene cerasin- orange and aniline-blue. Some observations on the spacial par- tition of the double refraction in agitated sols showed that in the eddies phenomena were ohserved which exhibited many analogies to the behaviour of uniaxial crystals in convergent light.These observat!ions serve as metliods for determining the flowing-double refraction and pleochroisiii and for determining the character of the sols. The rotation of the dark cross in eddies in opposition to the polarisation direction shows the direction of flow does not always need to correspond with the main vibration direction of the light. The coincidence of the dark Cross with the direction of polarisation in old vanadium pentoxide sols and soap solutions is attributed to the bending of the doubly refracting particles. The sign of the double refraction of soap solutions varies with the age and concentration of the sol.The change in the sign of the double refraction is explained as follows Colloidal particles in the form of short rods must arrange themselves with their symmetry axis CHEMICAL ABSTRACTS. S. I. L. A. A. E. Sols with Mon-spherical Particles.GENERAL SND PHYSICAL CIIEI\IISTRY. ii. 103 in the direction of flow particles in the form of leaflets must arrange themselves with the axis of symmetry a t right angles to this direc- tion. If now in the process of ageing the rods pass into leaflets then the optical character of the direction of flow must' a t first he the same as that of the colloidal particles and afterwards of the oppsite sign. Aniline-blue sols prepared by pouring an alcoholic solution of the dye into water show on flowing a strong negative double refraction in the red negative pleochroism in the region orange to green and a positive double refraction in the blue.Anomalous interference bands are produced by this anomalous behaviour. The optical anisotropy produced by a magnetic field has the opposite sign that is the colloidal particles arrange themselves a t right angles to the lines of force. On the other hand they arrange themselves parallel to the electrical lines of force. The negative double refraction of benzopurpurin can be made to disappear by heating. The addition of electrolytes causes the double refraction to reappear on cooling. The coagulum obtained by the addition of an excess of electrolyte gives a doubly refracting sol on peptisa- tion if the ad'dition of the electrolyte was slow or if the original sol was doubly refracting but if the coagulation took place rapidly or if the original sol was isotropic there will be no double refraction. When acidified double refracting red sols may be changed into double refracting blue sols.The strong pleochroism has always a negatlive sign and the particles of the sols are diamagnetic. The double refraction of vanadium pentoxide sols disappears more slowly the older and more concentrated the sol. Very concentrated old vanadium pentoxide sols and concentrated electrolyte-poor benzopurpurin solutions show a persistent double refraction similar to that of the crystalline liquids. The view of Diesselhorst and Freundlich (Zoc. cit.) that the growth of non-spherical particles is not a crystallisation but an aggregation of non-spherical primary particles in parallel layers is confirmed with the addittion that the primary particles may be crystalline and that eventually they may undergo crystalline processes.J. F. S. Recent Advances in Stereochemistry. B. I<. SINGH ( J . Proc. Asiatic Xoc. BengaZ 1921 17 213-230).-A general account of the historical development of stereochemistry and a discussion of the relation between optical activity and chemical constitution. Particular consideration is given to optical activity in homologous series the effect of conjugated nnsaturation and of position isomerism on optical activity. The Walden inversion is also discussed. H. W. Investigations on the Fundamental Law of Photochemistry. Y. LASAREV (2. physikal. Chem. 1921 98 94-97).-A theoretical discussion of work previously published on the bleaching of dyes by light (A.1912 ii 219; Ann. Physik 190'7 [iv] 24 661). The experiments on the bleaching in the presence of oxygen under increased pressures (up to 150 atm.) are particularly considered. The fundamental law for the bleaching of dyes has the formii. 104 ABSTRACTS OF CHEMICAL PAPERS. -dC/dt=cto(l-e-KC')(l-e-"~f~) in which C is the concentration of the dye K a constant proportional to the absorption constant C and K similar values for the substance non-sensitive to light and a the photochemical constant. It is assumed that in the reaction during the absorption of light an electron from the first Bohr orbit springs over to the furthest orbit. It is shown that the total absorption of light is proportional to the absorption of the largest (ionised) atoms.The increase in volume during photo- chemical reactions is explained by the assumption that the light inasmuch as it occasions an increase in the volume of the atoms by effecting the electron spring brings about an increase in the gaseous volume. J. F. S. New Measurements of Precision in the X-Ray Spectrum. M. SIEGBAHN (Compt. rend. 1921 173 1350-1352).-By the use of three spectrographs each adapted to a particular spectral region it was possible to measure a wave-length with an accuracy of 0-01-0.005~0 and by this means the wave-length of the copper line Ka was found to be 1537.36 x 10-11 em. in a vacuum. A more precise instrument is described the readings of which are accurate to within 0.002~0 and with this the value of A for Ka was found to be 1537.302 x em.W. G. Spectrographic Study of the De-intensifying of Barium Platinocyanide in the Villard Effect. A. ZIMMERN and E. SALLES (Compt. rend. 1922 174 80).-Fluorescent screens which have undergone the Villard effect can be regenerated by exposure to diffused light. It is shown that the radiations capable of de- stroying the Villard effect are found in four principal bands of almost equal breadth. The first is entirely in the infra-red the second in the greenish-yellow the third in the blue and the fourth in the ultra-violet. W. G. The Theory of Absorption of X-Rays by Matter and the Principle of Correspondence. LOUIS DE BROGLIE (Compt. rend. 19.21 173 1456-14&3).-An expression for the atomic coefficient of absorption of a substance for a radiation of wave- length A has previously been given (cf. A.1920 ii 208) in which the constant a was defined by the hypothesis that for the possible changes of internal configuration of an atom placed in a system in thermodynamic equilibrium a t the temperature T the probability A of the return of the atom from a configuration of energy fl to a configuration of less energy c2 is proportional to and also to the absolute temperature in such a way that ~412=M(E1-€2)T. A mathematical proof of the truth of this hypothesis and a means of calculating the constant a are given and it is shown that the coefficient of the Bragg-Pierce law is %t universal constant capable of being expressed as a function of the constants of the electron and of the radiation.Calculation of the X-Ray Absorption Frequencies of the Chemical Elements. I and 11. WILLIAM DUANE (Proc. Nut. Acad. Xci. 1921 7 260-267; 267-273).-1n the first paper W. G.GENERAL AND PHYSICAL CHEMISTICY. ii. 105 the author has calculated the K critical absorption frequencies of the elements magnesium sulphur calcium iron selenium molybdenum tin cerium dysprosium tungsten lead and uranium on the basis of the Rutherford-Bohr theory of the structure of atoms and the mechanism of radiation. The assumption is made that the electrons are distributed in circular orbits which do not lie in planes passing through the nucleus of the atom. In order to estimate the forces exerted on an electron in one orbit A due to the electrons in the parallel orbit B it is assumed that they are the same as if the charges are concentrated half at the nearest point to the orbit A and half a t the point furthest from A .A series of values is obtained which are in fair agreement with those observed. I n the second paper it is assumed that the forces are the same as if the electricity of the electrons in the orbit B is uniformly distributed along the orbit. The values calculated on the second assumption are somewhat smaller than those of the first calculations. The Laws of Absorption of X-rays. B. K. RICHTMYER (Physical Rev. 1921 18 13-30).-An experimental study of the absorption of X-rays by water (oxygen) aluminium copper molybdenum silver and lead each over a great part of the range of wave-lengths 0.093 8.to 0.95 d. The longest of these waves is shorter than the critical K absorption wave-length of oxygen aluminium or copper and falls between K and I; for molybdenum silver and lead. Rays from a Coolidge tube were analysed by a spectrometer with a sodium chloride crystal and the intensity was measured by ionisation of methyl bromide. Scattered and fluores- cent radiation from the absorbing screen were suppressed by placing the screen in front & the spectrometer slit nearest the tube. De- tailed tables and curves of the results are given. The rnass- absorption coefficients p / p of these substances is given by p/p= Ph3+(u/p) where h is wave-length and u / p is the mass-scattering coefficient except in the region close t o hR on the short-wave- length side where the equation gives values which are somewhat too large the error being greater as the difference between h and hg is smaller.For each substance P has a constant value for h<hg and another much smaller constant value for h>hK. The mass-scattering coefficient is independent of wave-length and is to a first approximalion the same for all element's. The atomic- absorption coefficient is given by pa=2.29 x 10-27 N413+~. where N is the atomic number and ca the atomic-scattering coefficient for A<hg. No trace of the suggested " J " absorption discon- tinuity was found. At 0.093 A. p / p for water is still much greater than for the hard rays of radium-C. The Luminescence of certain Oxides Sublimed in the Electric Arc. E. L. NICHOLS and D. T. WILBER (Physical Rev.1921 17 707-717).-Thin films of metallic oxides were obtained by subliming the metal or one of its salts from the crater of a direct- current carbon arc on to a metal disk. Oxides prepared by sub- limation are found to respond to excitation by cathode rays. J. F. S. CHEMICAL ABSTRACTS. 4"ii. 106 ABSTRACTS OF CHEMICAL PAPERS. The shift in colour with increasing temperature in luminescence is in general to the violet. The effect of pressure on luminescence is discussed. The most active oxides were those of calcium mag- nesium zinc zirconium silicon and aluminium. CHEMICAL ABSTRACTS. Anode Rays of Glucinum. G. P. THOMSON (Nature 1921 107 395).-The method of positive ray analysis applied to lithium (Aaton A. 1920 ii 344) has been extended to glucinum and found to yield a well-marked parabola corresponding with a single charge and an atomic weight 9.0 &0- 1 (Na= 23).No second parabola was observed which could be ascribed with certainty to glucinum but i t is doubtful if a line of intensity one-tenth that of the first could have been detected. No indieahion was found which would suggest that the atom of glucinum can lose two electrons under the prevailing experimental conditions. Reactions in Penetrating Radium Radiation and in Ultra- violet Radiation Filtered by Quartz Glass. 11. The Hydrogen Peroxide Equilibrium set up in Radium Radiation. ANTON KAILAN (2. phydcal. Chem. 1921 98 474-497; cf. A . 1912 ii 10 522; 1920 ii 576).-Radiation from 0.1 gram of radium metal after passing through 1 mm. of glass into 100 C.C.of water in contact with air produces a solution containing 6 x gram-equivalent of hydrogen peroxide ; in the presence of 0-01N- sulphuric acid the amount of hydrogen peroxide becomes and in 1.0N-acid the amount is 5x10-4 gram-equivalent. I n the last-named solution 6 x 10l2 and in the first 3 x 1012 molecules of hydrogen peroxide are formed per second. These values are considerably less than those obtained nine or ten years ago and reasons for the discrepancy are advanced. A comparison of the values obtained for the velocity of formation of hydrogen peroxide then and now with the rate of formation by other reactions which have been obtained in a similar manner to the present shows that both in aqueous and in non-aqueous solutions when the decom- position of hydrogen peroxide is neglected the number of mole- cules of hydrogen peroxide formed is of the same order as that of the ion pairs absorbed from the radiation by the medium.In ultra-violet light from a quartz glass lamp under similar conditions the reduction of the peroxide concentration by increase in the hydrogen-ion conckntration is less than in the radium rays whilst the decomposition of hydrogen peroxide is more than one hundred times greater than in the radium rays. Stationary Electron Vibrations without Radiation Resist- ance. A . D. FOKKER (Physics 1921 1 107-109).-1t is theoretically shown that a Bohr atom with electrons revolving jn closed paths may be free from radiation resistance without violating the principles of the classical theory.CHAGLES STAEHLING (Compt. rend. 1921 173 1468-1411; cf. A. 1920 ii 5).-In continuation of previous work (Zoc. cit.) it is shown that A. A . E. J. F. S. CHEMICAL ABSTRACTS. The Radioactivity of the Oxides of Uranium.CENEUL AND PHYSICAL CHEMISTRY. ii. 107 the radioactivity of the green oxide which has been restored to its original value commences to diminish as before. The restoration of activity may be brought about by simple calcination without passage through ammonium uranate. During this process of restoration the oxide undergoes loss in weight due for the most part to the removal of moisture. The black oxide which shows little loss in activity also shows little loss in weight or alteration in activity on calcination. The author considers that the green oxide exposed to the air in thin layers undergoes hydration as well as loss in activity the hydration diminishing the superficial density of the uranium atoms.The black oxides obtained by calcination at high temperatures do not hydrate and show little or no decrease in radioactivity. These facts tend to confirm the existence of a definite black oxide which is probably an allotropic modification of the green oxide. W. G. Isotopy of the Radio-elements and Meitner 's Nucleus Model. MAXIMILIAN CAMILLO NEUBURGER (2. physikal. Chem. 1921 99 161-167).-A theoretical paper in which on the basis of Meitner's nuclear hypothesis (A. 1921 ii 293) the author has subdivided isotopes into four groups. These are termed isotopes of the first second third and fourth order. Isotopes of the first order have the same nuclear charge and arrangement of the outside electrons but different nuclear mass total number of nuclear constituents arrangement of the nuclear constituents number of each kind of nuclear constituent and probability of disintegration ; radium and meso-thorium-I illustrate this group.Isotopes of the second order have the same nuclear charge arrangement of the outside electrons nuclear mass and total number of nuclear con- stituents but different numbers of each kind of nuclear constituent arrangement of the nuclear constituents and probability of dis- integration. An example of this class is furnished by ionium and uranium-Y. Isotopes of the third order differ only in the arrangement of the nuclear constituents and the probability of disintegration all other properties being identical ; this is the case with radium-D and actinium-B.Isotopes of the fourth order are identical in all the properbies mentioncd ; no examples of this class are known. J. F. S. Calculation of the Branching Relationships for Dual a-Disintegration and the Meitner Nucleus Model. MAXI- MILIAN CAMILLO NEUBURGER (2. physikal. Chem. 1921 99 168- 171; cf. Meitner A. 1921 ii 293).-A theoretical paper in which i t is shown that the method of calculation adopted by Smekal (A. 1921 ii 149) for determining the branching relationship is so closely dependent on the assumptions made as to the structure of the radioactive nucleus that it cannot possibly be of general use. The branching relationship cannot be calculated by this method since it leads to inaccurate values which lead to results opposed to the experimental data.The agreement found for the branching relationship by this method for the uranium radium thorium 4*-2ii. 108 ABSTRACTS OF CHEMICAL PAPERS. and actinium families with the experimentally determined values for this relationship is accidental. Emissivity of Iron and Copper. K. LUBOWSKY (Elektro- techn. Z. 1921 42 79-8l.).-The emissivity of both bright and blackened iron and copper was determined. Curves are given showing the effect of convection currents obtained from a flat plate of the material first perpendicular to and second in the direction of the air stream. Expressed in watts per sq. cm. per 1" of temperature excess the emissivity varies from 0.75 x to 1-5 x lob3 under the various conditions.CHEMICAL ABSTRACTS. The Effects of Impurities on the Ionisation Potentials Measured in Themionic Valves. L. S. PALMER (Radio Rev. 1921 2 113-125).-The method of investigation used is based on a study of the current-voltage curves measured in hard and soft 3-electrode tubes. The details of the method have been given in a previous paper. Certain bends in these curves are interpreted as being due to the bombardment of the filament by positive ions. The ionisation potentials of helium mercury and argon have thus been determined. There are variations in the values for the ionisation potentials obtained in helium. These are ascribed to impurities and the amount of impurity active accords with the values found by Horton in helium (A.1919 ii 210; 1920 ii 660; 1921; ii 672). This effect of the impurity also explains the low values of the potentials obtained by Stead and Gossling (A. 1920 ii 659). The characteristic of the soft 3-electrode tube can be used to determine the resonance and ionising potentials of the contained gas. The nature of the gas and presence of the impurities can be determined from the critical points of the characteristics. Methods of measuring ionisation potentials are liable to error if impurities are present. Horton's previous work is confirmed and the result has been extended to argon with traces of mercury. The value of the ionisation potential decreases slightly with increase of gas pressure causing changes in the characteristics similar to those for impurities. A number of critical potentials obtained for helium and argon are given.Estimation of the Radium Content of Radioactive Luminous Compounds. E. A. OWEN and WINIFRED E. PAGE (Proc. Physical SOC. 1921 34 27-32).-The absorption of 7-radiation in zinc sulphide has been measured by different methods and its value found to be approximately the same by all. No indica- tion was observed of the occurrence of an abnormal absorption when the radioactive salt was mixed with the sulphide. A table has been drawn up which gives the values of the ratio of the true to the apparent radium content for tubes of different diameters filled with a radioactive luminous compound. This table applies to a compound the apparent density of which is 2.03 grams per C.C. The value of the absorption of y-radiation from radium has been measured for zinc sulphide (OalOl) barium sulphate (0.079) barium chloride (0-loo) barium carbonate (00046) lead monoxide (0*294) J.F. 8. CHEMICAL ABSTRACTS.GENERAL AND PHYSICAL CHEMISTRY. ii. 109 bismuth sesquioxide (0.206) and uranium pentoxide (0.315) a The absorption coefficients are given in brackets in The mass absorption coefficient has been calculated in each case and it is shown that the barium salts have nearly the same value the mean value being 0.053. Electrical Conductivity of Salts and Mixtures of Salts. A. BENRATH and K. DREKOPF (Z. physikal. Chem. 1921 99 57-70).-The specific conductivity of molten mixtures of potass- ium sulphate with sodium sulphate magnesium sulphate potass- ium fluoride and lithium sulphate respectively has been determined Over the whole range of compositions and from the results relation- ships to the diagram of condition are drawn.It is shown that the conductivity isotherm can be deduced only to a small extent from the diagram of condition. It is also shown that the point a t which the eutectic appears is a well defined conductivity point. Pure salts as well as salt compounds change their conductivity with temperature according to the formula log k=a+bT. This formula is not generally applicable to mixtures of salts and mixed crystals; attempts to obtain a theoretical basis for the formula gave the relationship log k”+bT”=const. The formula of Tubandt log K=c-d/T is not generally applicable. For the complete explanation of the phenomena other factors particularly the viscosity must be known and taken account of in the calculation. The Electrical Conductivity of Anhydrides of the Higher Fatty Acids.D. HOLDE and IDA TACKE (Chem. Ztg. 1921 45 1246-1247; cf. A. 1921 i 842).-The values previously given for the molecular conductivity of oleic anhydride and oleic acid in acetone on being adjusted t o a dilution of 50 and 8 respectively gave 2 . 0 1 5 ~ 1 0 ~ and 0*53x104. If it is assumed that these two compounds are only slightly dissociated that is that the molecular conductivity increases ProportionalIy to the square root of the dilution the calculated figure for A for oleic acid becomes 1.33 x lo4 a figure not differing very greatly from that of the anhydride; the difference may be due to impurities in the acetone used. A.R. P. Measurement of Dielectric Constants. J. F. KING and W. A. PATRICK ( J . Amer. Chem. SOC. 1921 43 1835-1843).- A bridge method for the measurement of dielectric constants is described in which an arrangement consisting of an electron tube a condenser and an induction coil connected in a circuit serve as the source of alternating current of symmetrical wave form. Preliminary measurements of the dielectric constant of mixtures of ethyl alcohol with benzene ethyl ether and carbon tetrachloride respectively up to 100% by weight of alcohol are recorded. The dielectric constant increases with each addition of alcohol to the other constituent in a fairly regular manner. Electrical Moments of Carbon Monoxide and Dioxide Molecules. HANS WEIGT (Physikal.Z. 1921 22 643).-The J. F. S. 5. F. S. J. F. S.ii 110 ABSTRACTS OF CHEMICAT PAPERS. dielectric constants of carbon monoxide and carbon dioxide and their dependence on temperature have been determined with the object of ascertaining by means of the Debye theory the electrical moment of the two gases. The values obtained are p,,,=(0*1420&0.0017) x lo-" pc~=(0~l180-l-0~0016) x both of which are in good agreement with 6hat calculated from the Lorentz-Lorenz formula. J. F. S. Application of the Theory of Allotropy to Electromotive Equilibria. IV. A. SMITS (2. phgsilcal. Chem. 1921 98 455- 459 ; cf. A. 1915 ii 217 ; 1916 ii 77 ; 1917 ii 232).-The author offers a corrected interpretation of that published (" Theorie der Allotropie," Leipzig 1921,403405) for the electromotive behaviour of metals as soon as they are attacked by acids.The E.M.F. of M/Z-zinc sulphate dissolved in water O*05AT-sulphuric acid OalN- 0.5N- and l.0N-sulphuric acid and N-potassium sulphate has been determined a t 18" in an atmosphere of nitrogen. The results show that the potential of zinc is not effected by the presence of acid below 0 6 N and from this point upwards the potential is only changed by 2 millivolts. Similar experiments are described with zinc chloride in hydrochloric acid solutions; here it ii shown that a concentration of hydrochloric acid of 0.1N is without influence on the potential but that 0.5N and 1.ON cause a change in the E.M.F. of 0.021 and 0.038 volt respectively. Electromotive Behaviour of Aluminium. A.GUTNTHER- SCHULZE (2. Elelitrochem. 1921 27 579-582).-A reply to Smits in which the author maintains his previous assertions (cf. this vol. ii 20). J. 3'. S. Electromotive Behaviour of Metallic Compounds with Electron Conductivity. G . TRUMPLER (2. physikal. Chem. 1921 99 9-56).-Metallic or mixed conducting binary compounds combined with the metallic component as conductor and immersed in a solution of a salt of the metal which is saturated with the compound have a zero potential when measured against the metallic component in the same solution. The formula put forward previously by Haber for such Cases has been confirmed in the case of cuprous iodide and cuprous lead and silver sulphides. It is also shown that metallic and mixed conducting compounds combined with the metallic component as conductor possess the same potential as an indifferent electrode (platinum) when im- mersed in a solution saturated with these substances and containing the negative component both as ion and in the free condition.A necessary condition in this case is the stability of the compound towards the metallic conductor and the solution. This has been invest)igated in the case of lead cupric cuprous silver and ferrous sulphide against sodium sulphide and polysulphide solutions. If in the last case pure electrolytes are used the free negative component has no influence on the potential against the solution; this is much more dependent on the concentration of the com- ponents in the solution. This has been shown in the cells AgJAgBrJKBr,Br,(sat.) ; Ag]AgI[KI,I,(sat.).In the case of the J. 3'. S.QIEKERAI AND PHYSICAT CHEAIISTBY. ii. 111 mixed conducting silver sulphide in the presence of free sul- phur the potential lies between that of the pure components. This potential is a characteristic of the mixed conductor. The three forms of conductors metallic mixed and electrolytic are characterised by the potential relationship obtained by the above- named measurements. From the different behaviour of the metallic and electrolytic conductors (compounds) with respect to the influence of the negative component on the potential relations as obtained by the above method a fundamental difference of the internal structure is deduced according to which in the pure metallic conducting compounds the space lattice points are occupied by atoms or molecules and not by ions.They appear in opposition to electrolytes to be non-polar. It is shown that pure cuprous sulphide is an electrolyte or a mixed conductor in which the metallic component of the conductivity is very small. The passivity of lead sulphide in solutions of lead salt has been investigated and a process for activating the substance is put forward. The data in the literature on the solubility of lead sulphide and cupric sulphide are corrected. The electro- metric determination of the solubility of lead sulphide is not possible on account of the complete passivity of the lead electrode in sulphide solutions. The solubility product of lead sulphide has been determined approximately from the solubility in hydro- chloric acid and the value [Ph”]*[S”]=5 x obtained.It is shown that cupric sulphide is not stable in sodium sulphide and that in tlhe presence of copper only cuprous sulphide can exist in sodium sulphide solution and consequently the measurement of the copper potential in sodium sulphide solution does not give the solubility product of cupric sulphide (cf. Knox A. 1908 ii 830). The solubility product of cuprous sulphide is found to be [Cu’]2*[S”] =2 x 10-47. S. P. L. Trav. Lab. Carlsberg 1921 14 No. 14 pp. 31).-Biilmann’s quinhydrone electrode (A. 1921 ii 372) gives in the presence of sodium chloride too small a potential (with 3.99N-sodium chloride + 0.OlN-hydrochloric acid 0.6931 volt instead of 0,7044 volt a t 18”). This is due to a lowering of the solubility of quinhydrone and can be overcome by saturating the salt solution with quin- hydrone and with one of its constituents for example with quinol.This and various other questions are discussed theoretically in detail and the theory is verified by experiments. EINAR BIILMANN and HAKON LUND (Ann. Chim. 1921 [ix] 16 321-340).-It has previously been shown (A. 1921 ii 372) that aqueous solutions of quinhydrone may be used for the preparation of reversible electrodes with very constant potential which may serve to determine hydrogen-ion concentrations in solutions which are one-tenth molar. Concor- dant results are not obtained with stronger solutions. It is possibie to construct electrodes however in which the electromotive J. F. S. The ’‘ Salt Error ” of the Quinhydrone Electrode. SURENSEN M.S0RENSEN and K. LINDERSTRBM-LANG (Compt. rend. G. B. The Quinhydrone Electrode.ii. 112 ABSTRACTS 03 CHEMICAL PAPERS reaction is a transformation of one solid body into another solid body. The preparation of such electrodes with benzoquinone- quinhydrone and with quinol-quinhydrone is described. Such electrodes have hydrogenation potentials ~,,=0-7562 and 0.6179 respectively. They may be used for measurements over a wide range of hydrogen-ion concentration Electromotive Force produced by the Relative Displace- ment of an Electrode and an Electrolyte. ST~FAN PROCOPIU (J. Chim. Physique 1921,19,121-134).- It is found that the move- ment of an electrode in a liquid gives rise to an E.N.F. of move- ment which is general for all metallic electrodes.The dimensions of this E.M.F. are determined only by the solution pressure of the metal and the osmotic pressure of the metallic ion in the solution. The effects produced when a series of metals is moved in water nitric acid sulphuric acid salts of the metals and potassium hydroxide have been measured. The phenomenon is explained by the existence of a layer of solution round the electrode of composition different from that of the rest of the solution. This leads to a relationship between the photoelectric E.M.F. and that of movement and makes it possible to find the effect of movement on the electrical resistance of liquids. The Overvoltage of the Mercury Cathode. EDGAR NEWBERY Theory of the Electrolytic Ionic Condition and the Calcu- lation of the Electrolytic Solution Constants and of the Related Quantities from the Chemical Relationships.KARL FREDENHAGEN (2. physikal. Chem. 1921 98 38-69).-A theoretical paper in which it is shown that neither Arrhenius’s electrolytic dissociation theory nor Nernst’s theory of solution tension furnishes any information on the nature of the ionic con- dition or the nature of ionic dissociation. Neither of these theories can be directly deduced from the facts of inorganic chemistry and they do not bring these facts into relationship with one another The author has put forward an hypothesis of the iodc condition and the electrolytic solution constants which removes the above- named defects and shows how ordinary thermal dissociation passes into electrolytic dissociation. The hypothesis also shows how the solution constants of the elements and the partition and dissociation constants of chemical compounds may be calculated from the chemical relationships of the compounds and elements and from a factor which expresses the condition of the solvent.The hypothesis permits a qualitative deduction of the electrical and dielectrical behaviour of conductors of the second class. W. G. J. F. S. (T. 1922,121,7-17). J. F. S. An Electrolytic Current Intensification Effect a New Electrolytic Displacement Effect and the Connexion between Electrolysis and the Emission of Electrons in a Vacuum. 11. D. REICHINSTEIN and 3’. KLEMENT (2. physikal. Chem. 1921 99 275-289 ; cf A. 1921 ii 729).-A continuation of work previouslyUENERAL AND PI3YSIOAL CHEMISTRY.ii. 113 published. (Zoc. cit.). It is shown that in a closed circuit by means of superimposed alternating current a stronger direct current can be produced the work from which can be greater than that of the alternating current used to generate it. The action of a high frequency Ourrent on an electrolytic cell is not a specific high frequency action; qualitatively it is the same as that of a low frequency current. A11 passivity phenomena both anodic and cathodic show on superposing an alternating current on the direct current a decrease of the direct current polarisation and thereby allow themselves to be used as detectors or current intensifiers. Using the commutator method an intensification of two hundred times has been obtained and the experiments indicate that this may be still further increased. A new experiment with a highly evacuated electron tube is described which indicates that after removal of the polarisation it is possible to generate cathode rays with low potentials and cold electrodes.11. J. N. BR~NSTED (K. Danske Videnskab. Selskab. Math.-fys. Medd. 1920 3 1-21 ; cf. A. 1920 ii 78).-By a modification of the original electrometric method consisting in the use of a streaming electrode E.M.P. determinations have been carried out with one electrolyte dissolved in a concentrated solution of another. Cells solvent (n-cl) solvent (n-c,) AgC1,Ag and Of the ' Ag'AgC1 1 chloride ( c l ) I chloride (cz) I (n-c2) Ag were employed. Support is afforded to the theory that the simple gas laws are valid for ions present; in salt solutions the concentrations of which are large in comparison with that of the ions concerned.Conditions under which the law fails to apply are discussed and the results of Loomis Essex and Meacham (A. 1917 ii 353) that slight changes in the activity coefficient occur with varying concentrations are confirmed. CHEMICAL ABSTRACTS. Newer Investigations on the Anomaly of the Strong Electrolytes. LUDWIG EBERT (Jahrb. Radioaktiv. Elektronik 1921 18 134-196).-An alphabetical bibliography of the work on strong electrolytes is given. The whole subject of the behaviour of strong electrolytes is discussed under the headings (i) chief anomalies and (ii) the hypothesis of complete dissociation of the strong electrolytes and the activity of electrical forces between the ions.J. F. S . Transport Numbers of Sulphuric Acid by the Concentra- tion Cell Method. ALFRED L. FERGIUSON and WESLEY G. FRANCE ( J . Amer. Chem. SOG. 1921 43 2150-2160).-A method is described for the determination of the transport numbers of a uni- bivalent electrolyte by measurement of the potentials of con- centration cells. The transport number of the anion of sulphufic acid for concentrations between 0.1M and 0.01M has been measured and found to be 0.1868&0.0007 a t 25". This value is compared J. F. S. Applicability of the Gas Laws to Strong Electrolytes. I I silver salt (cl) silver salt (cz) solvent (n-cl)ii. 114 ABSTRACTS OF CHEMICAL PAPERS. with the values obtained by other investigators. It is shown that the dissociation values determined from freezing-point data are more satisfactory for calculating the potentials of concentration cells than those obtained from conductivity data.A correction to the formula for the potential of a concentration cell has been developed which takes into account the undissociated part of the acid. It is shown that the concentration cell method is entirely satisfactory for the determination of the transport numbers of sulphuric acid. J. F. S. Influence of Gelatin on the Transport Numbers of Sulphuric Acid. ALFRED L. FERGUSON and WESLEY G. FRANCE ( J . Amer. Chem. Soc. 1921 43 2161-2171).-The effect of gelatin on the transport numbers of gelatin has been investigated. It is shown that the addition of sulphuric acid up to 20% increases the transport number of the anion of sulphuric acid (0-1-0-01M) from 0.187 in the absence of gelatin to 0,685 in the presence of 20% gelatin.The effective concentration of O-lM and 0.01M sulphuric acid solution is reduced by the addition of gelatin. The conductivities of sulphuric acid are reduced by the addition of gelatin. An hypothesis is put forward to account for the action of gelatin in the presence of electrolytes. Ek?ctro-QsmOsis. A. 13. W. ATEN (Chem. Weelcblad 1921 18 690-692) .-The theory of electro-osmosis of liquids through porous solids is discussed and the volume passing in unit time shown to be directly proportional to the current density the dielectric constant of the liquid and the potential difference between the liquid and the porous material and inversely proportional to the viscosity and conductivity of the liquid.The various attempted technical applications of the phenomenon and of kataphoresis (which term is restricted to the motion of solid particles suspended in a liquid under the influence of the electric field) are described. s. I. L. J. F. S. Some Electro-osmotic Experiments with do Haen's Membrane Filters. P. H. PRAUSNITZ (Kolloid Z. 1921 29 293-309) .-The electro-osmosis of water solutions of ammonia sulphuric acid ammonium sulphate sodium sulphate potassium ferricyanide and aluminium sulphate through de Haen filters for varying size of pores has been investigated a t 25" and under a pressure of 43 em. of water. It is shown that the de Haen filters are particularly well adapted to the study of the influcnce of electrolytes on electro-endosmosis.Filters of medium-sized 1:ores (Nos. 20 and 320) when 5 em. thick allow 100-500 C.C. of water to pass per hour under the pressure used in the experiments. Dis- tilled water ( A = 6 x lo+) travels toward the cathode through the mem- brane under a current of 100 volts and about 0.1 ampere at the rate of 1-2 litres per hour. The addition of sulphuric acid to the anode compartment or any addition of thorium chloride or aluminium sulphate reduces the electro-endosmosis to values below thzt of water and in cases may produce even a weak anodic endosmosis. InGENERATI ANT) PRYSICAT CIIIEMISTRY. ii. 115 other cases the addition of electrolytes brings about an increased cathodic endosmosis in which the amount of water transported varies with the time the current is flowing and the nature and concentration of the electrolyte. It is shown that in general with an electrical conductivity of 2 0 0 4 0 0 x 10+ and a consump- tion of energy of 0.01-0.06 K WHllitre of transported liquid 8-16 litres/hour of liquid can be made to pass through a dia- phragm of 100 cm.2.It is not always necessary that the electrolytc should pass through the membrane as such; particularly in the case of ammonia it is shown that the addition of the base to the cathode compartment can bring about a very considerable endos- mosis of the water which is to be attributed to the wandering in the opposite direction of those ions which are responsible for the discharging of the membrane. The transport of the SO,-ion through a de Haen membrane from negative to positive compart- ments brings about a considerable passage of water from the positive to the negative compartment.In every case there is an optimum electrolyte concentration and if this is exceeded anomalies occur which are found to be connected closely wit'h the electrical conductivity. The discharge of the membrane is held to be. due in all probability to the adsorption of hydroxyl ions for all processes which effect a reduction of the hydroxyl-ion concentration also effect a reduction of the electro-endosmosis (cf. D.R.-P. 333575 1919). Attainment of Constant High Temperatures. E. MOSER (2. angew. Chem. 1921 34 625).-The apparatus or object to be maintained a t constant temperature is immersed in paraffin con- tained in a cylindrical glass vessel surrounded by an outer glass vessel of similar shape but enlarged to a spherical form a t the bottom to accommodate a liquid of suitable boiling point which is kept in ebullition so that its vapour surrounds the inner vessel.The two vessels are sealed together round the top except where a tube serves to connect the vapour jacket with a reflux condenser. The lower end of the condenser tube projects downwards for some distance into the vapour jacket and the vapour enters it fhrough a lateral orifice. The end of the tube is drawn out to a jet and disposed vertically above the boiling liquid. By this arrangement the condensed liquid is warmed again before it falls back into the jacket and is prevented from falling on the hot walls of the vessels. Liquids of high boiling point such as ethyl benzoate b.p. 212-,5" The Expansions of some Refractory Materials at High Temperatures. B. BOGITCH (Compt. rend. 1921 173 1358- 1360) .-The expansion curves for bauxite clay silica chromite and magnesia over the temperature range 0" to 1600" are given. The smallest expansion was shown by the bauxite which is suitable for use in furnaces subject to sudden changes in temperature Silica showed the most irregular expansion ; it expanded rapidly up to 600" and then only very slowly and above 1000" showed a slight contraction. The curve shows two singular points a t 210" J. F. S. have been successfully used in the outer vessel. J . H. L.ii. 116 ABSTRACTS OB CHEMICAL PAPERS. and 570" respectively which are the transformation points of cristobalite and quartz. Furnaces constructed with such bricks must only be heated up very slowly the temperature rise being less than 50" per hour.The curve for the clay bricks is intermediate between the curves for bauxite and silica. Magnesia and chromite showed the biggest expansions and such bricks are only suitable for the construction of furnaces in continuous work. Coefficient of Expansion of Molten Salts. W. HERZ (2. physikal. Chem. 1921 98 98-102).-1n previous papers (A. 1914 ii 25 245; 1921 ii 381) it has been shown that Mendeldev's equa- tion is true for the expansion of normal organic liquids. In the present paper the equation has been applied to the molten inorganic substances sodium molybdate lithium nitrate sodium nitrate rubidium bromide czsium nitrate potassium tungstate czsium iodide potassium molybdate sodium tungstate rubidium fluoride caesium sulphate and thallous nitrate.The data employed are taken from the work of Jaeger (A. 1918 ii 33). The densities calculated by the Mendelgev formula agree in most cases to about 1 per 1800 with the experimental values. The only cases where divergence is shown are thallous nitrate and sodium tungstate and here it is not much greater than in the other cases. The density values calculated by the Mendeldev equation are compared with those calculated by Jaeger (Zoc. cit.) by a single constant formula for caesium iodide and rubidium fluoride and by a two constant formula for caesium sulphate and the value of the single constant Mendelgev formula demonstrated.General Methods for the Determination of the True Mole- cular Constitution of Pure Substances and their Mixtures. MARIO BASTO WAGNER (2. physikal. Chem. 1921 98 81-93).-A theoretical paper in which the author differentiates between the thermodynamics of mixtures treated in connexion with their independent components and the thermodynamics of mixtures treated in connexion with their true components. The advantages and drawbacks of both methods of treatment are explained and the nature of the results obtainable is pointed out in each case. The various properties which may be used in the determination of constitution are enumerated and their application is indicated. These include volume heat change vapour pressure solubility freezing point boiling point specific heat compressibility thermal coefficient of expansion and osmotic pressure.The properties dielectric constant viscosity refraction and surface tension do not permit conclusions being drawn which may be used in the second method of treatment. Thermodynamics of Mixtures. IX. MARIO BASTO WAGNER (2. phy?ilcal. Chem. 1921 98 151-156; cf. A. 1921 ii 375).-A theoretical paper in which the theory of the heat of mixtures is developed on the basis of the thermodynamics of mixtures treated in connexion with the true components (cf. preceding abstract). J. F. S. W. G. J. F. S. J. F. S.GENERAL AND PIXYSICAL CHEMISTRY. ii. 117 Theory of Equations of State. 11. MARIO BASTO WAGNER (2. physikal. Chem. 1921 98 24G251; cf. preceding abstract).- The hypothesis developed previously is extended.The present paper deals with the theory of the heat of vaporisation and the internal pressure. J. F. S. Equation of Condition of Nitrogen at Small Pressures and Low Temperatures. R. BARTELS and A. EUCKEN (2. physikal. Chem. 1921 98 70-79).-The equation of condition of nitrogen has been measured by means of a constant pressure gas thermometer between the temperatures 90" and 76" Abs. and between the pressures 0.5 and 1-0 atm. The results are repre- sented by means of an empirical formula for the corkection quantity B' of the form v=RT/~-RTB'. This formula has been used to calculate the molecular heat of nitrogen for the ideal gas con- ditions and the value 6.873 obtained for Cp. This value is 0.07 cal. or 1 yo lower than that (6.944 cal.) demanded by the classical theory whilst the Berthelot equation of condition leads to a value 0.2 cal.lower than the classical value for the temperature 92" Abs. A comparison of the reduced B' values for a range of temperature shows that the curves for hydrogen and nitrogen cannot be brought into coincidence but that at low temperatures they diverge. J. F. S. Equation of Condition. II. Principal Equation of Con- dition. 111. Principal Equation of Condition and the Equation of Condition for Individual Substances. IV. Compressibility Equations of Liquids. A. WOHL (2. physikal. Chem. 1921 99 207-225 226-233 234-241; cf. A. 1914 ii 430).-A series of theoretical papers in the first of which the author further develops the equation of condition previously published (loc. cit.).The various relationships brought out by this equation are considered and compared with the equations of van der Waals and Kamerlingh Onnes. I n the second paper equations of condition are developed and considered for helium hydrogen water and ethyl alcohol. The third paper deals with compressi- bility equations for liquids particularly highly compressed sub- stances. The substances ethyl ether carbon dioxide and hydrogen are considered. J. F. S. Extension of Ebullioscopy and its Application to Binary Mixtures. EBNST BECKMANN and OTTO LIESCIIE (2. physikal. Chem. 1921 98 438454).-The authors have combined the Raoult equation P=Po[N/(N+n)] with Dalton's law P=B[N'/ (N'+n')] to form the equation Po[N/(N+n)]=BIN'/(N'+n')] and shown that this equation may be used generally in the ebullioscopy of binary mixtures and may be extended to meet complicated cases since the determination of the absolute boiling point fixes the value of Fo with the help of vapour pressure tables or formula.The introduction of the boiling point difference A and the ebullio- scopic constant E leads t o a special ebullioscopic equationii. 118 ABSTRACTS OF CIIEMlCAL PAPERS. A=E(n-n') which may only be used for small A values. If in either of the above equations n or n' is given the value zero the two limiting cases are obtained in which the second component (represented by small letters) is non-volatile or is not soluble in the first component. J. F. S. A Vapour Pressure Formula with a General Integration Constant. F. A. HENGLEIN (2. physikal.Chem. 1921,98,1-13).- A theoretical paper in which the constants of a previously pub- lished rule (A. 1920 ii 732) €or the comparison of the vapour pressure curves of two substances log T,=a log T,+b have been brought into relationship wit'h the Trouton constants. From this relationship a vapour pressure formula has been deduced which contains two specific constants and has the form log p(atm.) = - k/T,'+ 4.6222. The formula holds in comparison with other two constant vapour pressure formulq over greater temperature ranges and is characterised by the fact that the integration constant is the same for all substances. The index n is shown to be equal to ~ / ( v - - v ' ) p . K where K has the same value €or all substances and consequently A/(v-d)p may be calculated from the above formula; on the other hand n may be determined from A/(v-d)p or AIRT.To calculate the actual formula two vapour pressure determinations are neces- sary or the knowledge of one vapour pressure point and the molecular latent heat of vaporisation a t the same pressure. The formula is shown t o be equally true for sublimation pressures and it may also be applied to decomposition pressures. Theory of Binary Mixtures. VII. Mixtures of Ethyl Ether and Bromoform. F. DOLEZALEK and M. SCHULZE (2. physikul. Chem. 1921 98 395-429; cf. A. 1920 ii 32).-The vapour pressure of a series of mixtures of ethyl ether and bromo- form has been determined a t 25" and 75" ; the contraction on mixing the coefficient of expansion and the density of the mixtures have been determined a t 25".The results show that on mixing the components a mutual partial complex formation occurs. The resulting compound consists of one molecule of ether and one molecule of bromoform; it occurs in the solution in a dissociated condition and on heating it decomposes. Bromoform itself is strongly associated but with decreasing concentration the associa- tion decreases. The vapour pressure was determined by a new static method. A theory is developed whereby the molecular constitution may be calculated from the vapour pressure measure- ments. From two measured vapour pressures the combination constant K and the association constant k were determined and from these the molecular constitution of the mixture was calculated for 25". The results show that a t 25" bromoform consists of 65% of bimolecules and that in the mixture of 1 mol.of ether and 1 mol. of bromoform 23% of the eyui-molecular compound is present. The vapour pressure for ail mixtures has been calculated from the molecular composition and found to be in good agreement with the experimental values. A marked coritraction occurs on mixing J. F. S.GENERAL AND PHYSICAL CHEBLISTRY. ii. 11.9 ether and bromoform the contraction curve is strongly depressed on account of the association of the bromoform. The contraction has been calculated on the basis of the theory and found to agree with the observed contraction. Prom the coefficient of expansion the contraction a t 15" 20" and 30" has been calculated. From the contraction a t 25" the density of the mixtures was calculated and the results show that the measurement of volume change by the differential method is the most exact for the measurement of easily volatile liquid mixtures.Vapour Pressure of Binary Mixtures. GERHARDT C. SCHMIDT (2. physilcal. Chem. 1921 99 71-86).-A new simple static method of measuring the vapour pressure of liquids is described. It is shown that the dynamic method of measuring the vapour pressure of mixtures gives only moderate results and then only when the experiments are made under definite conditions and it is inferior in every way to the new static method. The vapour pressures of the following mixtures benzene-ethyl ether benzene-chloroform benzene-methyl acetate methyl acetate- ethyl acetate benzene-carbon disulphide benzene-toluene toluene- carbon disulphide ethyl alcohol-methyl alcohol benzene-methyl alcohol chloroform-carbon disulphide and acetone-chloroform have been measured up to a pressure of 4 atmospheres.By plotting the molecular compositions as abscissz and the vapour pressures as ordinates it is found that a t all temperatures (20-100") mixtures of ethyl alcohol and methyl alcohol give a straight line. Mixtures of benzene and ether and of benzene and chloroform give approximately straight lines up to 30" but a t higher temperature curves which a.re convex to the abscissa axis and the higher the temperature the greater the convexity. Mixtures of acetone and chloroform a t 0" give a straight line and a t higher temperatures curves convex to the abscissa axis which become more convex as the temperature is raised.Mixtures of benzene and toluene ethyl acetate and methyl acetate and benzene and methyl acetate at low temperatures give straight lines but a t higher temperatures the curves are concave to the abscissa axis and the concavity becomes greater as the temperature is raised. Mixtures of benzene and carbon disulphide toluene and carbon disulphide chloroform and carbon disulphide and benzene and methyl alcohol give at 0" curves which are concave to the abscissa axis and the higher the temperature the greater the concavity this being particularly noticeable in the case of benzene- methyl alcohol. From the fact that the higher the temperature the greater the concavity or convexity the conclusion can be drawn that for every liquid mixture there is a temperature a t which the relationship between the vapour pressure and the molecular com- position may be represented by a straight line generally speaking this occurs at low temperatures.It is shown tha.t a series of deduc- tions from Dolezalek's theory of binary solutions which refer to the influence of temperature on the course of the isotherms are not confirmed by the experiments. Consequently the theory cannot be maintained. J. F. S. J. F. S.ii. 120 ABSTRACTS OF CHEMICAL PAPERS. Intersecting Vapour Pressure Curves and Deductions therefrom. CARL VON RECHENBERG (2. physikal. Chem. 1921 99 87-104).-A large number of pairs of substances are recorded for which the vapour pressure curves intersect. From a comparison of the intersecting vapour pressure curves the following conclusions are drawn.All liquid and solid substances consist of large molecular complexes of undetermined variable composition of different stability and present as many classes of compounds as they have different molecular types. Every individual com- pound behaves in a characteristic manner. The division of liquids into associated and non-associated groups from surface tension measurements is incorrect. All compounds are associated but the so-called associated compounds are more loosely combined. The sub-division only separates the most divergent compounds but does not take account of the intermediate and transition com- pounds. A table is drawn up of the various aggregates according t o the increase of vapour pressure with increase of temperature.The table is very similar to Rothmund's solubility table from which it follows that vapour formation and solubility are parallel phenomena and must be due to the same cause. Vaporisation of Solutions of Liquid Pairs possessing Intersecting Vapour Pressure Curves. CARL VON REGHENBERG (2. physikal. Chm. 1921 99 105-115 ; cf. preceding abstract).- The Bancroft rule that liquids with intersecting vapour pressure curves form solutions with a characteristic point has been con- fimed when notice is taken of the fact that the property of the characteristic solution only obtains inside a limited pressure region. A large number of homogeneous mixtures with intersecting vapour pressure curves are tabulated with the minimum boiling point and the concentration of the characteristic fraction a t 760 mm.J. F. S. J. F. S. Distillation and Rectification. L. GAY (Chim. et I d . 1921 6 567-578 ; cf. this vol. ii 85).-In order to obtain the maximum efficiency from a column ceteris paribus the higher the tem- perature of the initial mixture the lower should be the level of its introduction into the distillation apparatus. This level should be such that an initial liquid or gaseous mixture meets a liquid or gaseous mixture of approximately the same composition in the column. If the liquid mixture is a t its boiling point or rather if the gaseous mixture is a t its condensation point then the com- position of the two mixtures is identical. The determination of the minimum intensity of heat and the minimum number of com- partments of the column necessary for an initial gaseous mixture has been carried out in a similar manner to that used for an initial liquid mixture (Zoc.cit.) and applied to the separation of practically pure water and alcohol from any gaseous mixt,ure of water and alcohol at 95". The determination of the minimum intensity of heat necessary t o remove a trace of impurity from a liquid has also been carried out. F. M. R.GENERAC AND PHYSICAL CHEMISTRY. ii. 121 Heat of Formation of Silver Iodide. HUGH STOTT TAYLOR and WILLIAM THEODORE ANDERSON jun. (J. Amer. Chem. Sec. 1921 43 2014-2017).-Eraune and Koref's calorimetric measure- ment of the heat of formation of silvcr iodide (A. 1914 ii 536) using AT-potassium cyanide instead of 3N-solutions as solvent for silver iodide have been repeated.The result 15,100 cal. per mol. of silver iodide has been obfained which confirms Braune and Koref's value. J. 3'. S. Relationship between Heat of Solution and Heat of Fusion of Organic Substances. GEORG GEHLHOBF (2. physikal. Chem. 1921,98,252-259) .-The heat of solution of naphthalene diphenyl diphenylamine azobenzene a-naphthylamine p-naphthylamine urethane paraffin (wax) nitronaphthalene nitrophenol m- dinitro - benzene phenol menthol thymol pyrogallol resorcino1 citric acid and chloral hydrate has been determined in 1-3% solutions in the solvents water benzene ethyl ether alcohol carbon disulphide acetone amyl acetate aniline chloroform and acetic acid. The results show that for a series of substances particularly hydro- carbons aromatic amines urethane and azobenzene the heat of solution in various solvents is practically identical with the heat of fusion.Organic substances containing the hydroxyl group give very different values for the heat of solution and the heat of fusion whilst substances containing the nitro-group take up an intermediate position between the other substances. The heat of solution of the sodium potassium and ammonium haloids has been deter- mined in aqueous solution and the results are discussed in con- nexion with the structures and space lattices of these salts. J. P. S. Heats of Solution and of Transformation of the Acido- and Aquo-cobalt Pentammines. ARTHUR B. I A M B and JOHN P. SIMMONS ( J . Amer. Chem. SOC. l921,43,2188-2199).-A method of calorimetry has been developed in which only observations 011 a silver coulometer and of time and electrical resistance are required.It is shown that the same cobalt sulphide CopS3 is produced by the action of sodium sulphide on chloro- and aquo-pentammine- cobalt chloride in aqueous solution. The solubility of chloro- pentami~inecobalt chloride in water a t O" 30° and 58" has been determined and the values 2.244 6.047 and 10.01 respectively have been obtained in grams per litre. The heat of solution has been calculated from these data and the vdue 13,440 cal. obtained which is in fair agreement with the experimental value. 12,400 cal. The heats of solution of a number of acido- and aquo-pentammine- cok)alt salts in water have been measured. The following values are found a t 25" in cals.chloro-chloride -12,420 ; aquo-chloride -6,460 ; bromo-bromide - 12,660 ; aquo-bromide -9,220 ; nitrato-nitrate - 14,900 ; and aquo-nitrate - 15,300. The heat of reaction of solutions of pentammine saks with solutions of sodium sulphide has been measured at 25" and that of the solid salts with sodium sulphide solutions calculated. Theii. 122 ABSTRACTS OF CHEMICAL PAPERS. following values in cals. a t 25" are obtained chloro-chloride 15,070 ; aquo-chloride 12,930 ; bromo-bromide 13,290 ; aquo- bromide 11,600 ; nitrato-nitrate 12,340 and aquo-nitrate 11,860. From these results the heat of transformation of the acido-salt to the aquo-salt in each case has been calculated and the values chloride 2,140 cal. ; bromide 1,690 cal. and nitrate 480 cal.have been obtained. J. F. S. Heat of Wetting of Silica Gel. W. A. PATRICK and F. V. GRIM ( J . Amer. Chem. Xoc. 1921 43 2144-2150).-The heat change occasioned by wetting silica gels with water ethyl alcohol benzene carbon tetrachloride and aniline respectively has been determined a t 25". The quantity of liquid used in each experiment was 50-07 C.C. and the amount of gel 2-3-2.5 grams. The follow- ing values in cals./gram of gel were obtained water 19.22 ; alcohol 22.63 ; benzene 11.13 ; carbon tetrachloride 8.42 and aniline 17.54. The heats of wetting have been discussed and found to be in keeping with the changes of surface energy. J. F. S. Viscosity of Gelatin Sols. ROBERT H. BOGUE ( J . Amer. Chem. Xoc. 1921 43 1764-1773).-A number of experiments have been effected with gelatin sols to determine the relation between viscosity and concentration.The data obtained have been applied to Hatschek's formula for the viscosity of emulsoids and it is shown that the value of A'IA representing the volume occupied per unit weight of dispersed phase is not a constant with varying concentration but rises regularly to a maximum and thereafter regularly diminishes with increasing concentration. This behaviour is not,iced also in the case of other colloids. A tentative explanation is presented based on the effect which increas- ing concentrations of dispersed phase will have on the surface tension of the dispersion medium. Assuming the equilibrium surface tension solvation potential an empirical relation is developed which with a fair degree of accuracy defines the equi- librium.At very high concentrations a reversal of phase probably occurs a t which no expressions yet developed adequately represent the relations involved. A high degree of solvation is shown to be indicated by a high coefficient of viscosity that is solvation and viscosity are parallel functions. Isoelectric gelatin at a hydrogen-ion concentration 2x10-5 is shown to have the lowest viscosity and the lowest degree of solvation gelatin chloride a t a hydrogen-ion concentration 3.1 x the highest and calcium gelatinate a t a hydrogen-ion concentration 2.5 x is intermediate. If an excess of acid is allowed to remain in the gelatin solution even although the acid be of very low concentration the viscosity and degree of solvation will be reduced.A New Viscostalagmometer for the Estimation of Surface Tension and Viscosity of Liquids of Very Different Limpidity. I. TRAUBE (Biochem. Z. 1921 120 106-l07).-The essential feature consists in the adaptation to the ordinary form of stalagmo- ,J. F. 8.QENERAL AND PHYSICAL CHE3TISTRY. ii. 123 meter of five interchangeable ground-in mouth-pieces of differ- ing capillary bore thus allowing measurements to be performed with the same apparatus on liquids of a great range of fluidities. H. K. Ionisation and Surface Activity of Aqueous Solutions of Aliphatic Acids. WILH. WINDISCII and PHIL. OSSWALD (2. physikal. Chem. 1921 99 172-188).-The connexion between ionisation and surface activity of organic acids has been investigated. It is shown that of N/lO-acid or alkali when added to an aqueous solution acts only as a diluent that is the surface activity is independent of the hydrogen-ion concentration. Experiments have been made to determine the concentration of acids of different strengths such as hydrochloric formic and acetic acids which must be added to solutions of nonoic acid so that the same size of drops may be obtained and also the concentrations of these acids which will produce the same colour with methyl-orange solution.It is shown that free nonoic acid in aqueous solution is 10% dissociated and therefore the addition of acid increases it,s surface activity. The simultaneous presence of sodium chloride is without action on the activity. With continued addition of acid the size of the drops sinks to a constant minimum.A solution of sodium nonoate exhibits a small activity because through hydrolysis a small quantity of acid exists in the free condition. By the addition of a small quantity of alkali the free molecules are ionised and the size of the drop sinks to that of water. An addition of hydrochloric acid produces fresh acid molecules and the size of the drop sinks to a minimum which is reached when all the aliphatic acid ions have disappeared. Consequently it follows that the surface activity of aqueous solutions of aliphatic acids is due to ionisation processes and the possibility of calculating the size of the drops due to the action of various additions is pointed out. J. F. S. High Pressure due to Adsorption and the Density and Volume Relations of Charcoal.WrrmAni D. HARKINS and D. T. EWING ( J . Amer. Chem. SOC. 1921 43 1787-1802).-The present paper furnishes evidence in favour of the hypothesis pre- viously expressed (A. 1921 ii 87) by the authors which states that the liquids which penetrate into charcoal are compressed by a force due to molecuIar attraction which acts as a pressure of many thousand atmospheres (20,000 or more). The present paper shows that it is the liquid in the micro-pores and not the macro- pores which is compressed and consequently the pressure mould probably be much greater than the figure mentioned. Kot only charcoal but other porous substances and fine powders should exert this compressive effect but to a much smaller extent. A number of experiments are described in which the compression is demonstrated by volume changes but the values measured have not exceeded 72 atlms.Ethyl ether which is much more compressible than water occupies a volume in charcoal which isii. 124 ABSTRACTS OF CHEMICAL PAPERS about lOyo less than that occupied by the amount of water which outside the charcoal is equal in volume to the ether. It is probable that the water in the micro-pores is compressed by about 25% or more whilst the ctlicr is compressed by 40%. The liquids in tho macro-pores of the diameter 1 * 2 ~ l O - ~ em. are not compressed sufficiently to produce a noticeable effect on the volume. The true volume relations in 1 C.C. of a characteristic coconut shell charcoal are 0.28 C.C. micro-pores 0.18 C.C. macro-pores 0.54 C.C. carbon which give a density of 1.60 for the carbon.The density of the lumps of such a charcoal is 0.866. Charcoals which are inactive as adsorbents of gases do not exert a compressive effect on the adsorbed liquids of a sufficiently high magnitude to be very evident although there appears to be a slight effect of this nature. The densities of the carbon in the two inactive wood charcoals investigated are 1.65 and 1.50. When coconut-shell charcoals alone are considered it is found that the lower the apparent density in an organic liquid the less is the adsorptive action on vapours and it is indicated that this relation may be expected to hold better the more compressible the liquid which is adsorbed so that either ethyl ether or pentane or another highly compressible liquid should be used in such tests.Simple thermodynamic equa- tions are given for the heat of immersion or adsorption of a plane surface. Whilst there is probably no definite area of surface inside a lump of charcoal a definition for an apparent area may be given. The one chosen here is that the apparent area with respect t o the heat of immersion is the area of the plane surface of carbon which will develop the same amount of heat on immer- sion as is equal to that developed by the immersion of 1 gram of the charcoal in the same liquid. Since the film in the charcoal is probably a number of molecules thick this apparent area is prob- ably larger than corresponds with the carbon surface. This method indicates that the area of 1 gram of charcoal is 120 sq. metres.The magnitude of the heat of immersion of liquids on mercury is 3.3 x 10-6 cal. for octane sncl 3.25 x cal. for isobutyl alcohol. J. F. S. The Origin of the Potential Differences Responsible for Anomalous Osmosis. ~ACQUES LOEB ( J . Gen. Physiol. 1921 4 213-226).-1f a collodion bag coated on the inside with protein (gelatin) separate two identical acid solutioiis and a neutral salt be added to the inside the rate of diffusion inwards through the membrane is a minimum a t the isoelectric point of the protein increases with the acidity to a maximum and then decreases. The potential difference bettween the two solutions varies similarly. In the absence of protein these characteristic variations are not obtained. The anomalous variation of the potential difference is apparently n consequence of the Donnan equilibrium between solution and protein and this potential difference causes electrical endosmosis and hence the irregular rates of diffusion.The potential difference is also influenced by the diffusion potential but this exists although no protein is present. W 0. K.GENERAL AND PEYSICAL CXlEMISTRY. ii. 125 Penetration of Electrolytes into Gels. 111. Influence of the Concentration of the Gel on the Coefficient of Diffusion of Sodium Chloride. WALTER STILES and GILBERT SMITHSON ADAIR (Biochem. J. 1921,15,620-626).-The coefficient of diffusion from normal solution into gelatin and agar gels was measured by the indicator method previously described (A. 1920 ii 235). With increasing concentration of gel the coefficient of diffusion at first decreases rapidly according to an exponential relation but with concentrations above 2% the curve connecting coefficient of diff u- sion and concentration is approximately a straight line.It is shown how this result can be harmonised with the relation between diffusion and viscosity found by Einstein Sutherland and von Smolukowski. The diffusion coefficients found when extrapolated for diffusion in water are about 7.5% higher than those obtained from the results of Oholm (A. 1905 ii 147). This is attributed to the fact that in Oholm's experiments the salt concentration refers to ionised+un-ionised salt whereas the authors measure only the rate of penetration of the ions which diffuse about twice as fast as the un-ionised salt. The resistance which even a stiff jelly offers to salt diffusion is quite small; the rate is reduced by less than 2y0 for each gram of gelatin added to 100 C.C.when the concentration exceeds 2%. G. B. Penetration of Electrolytes into Gels. IV. Diffasion of Sulphates. WALTER STILES (Biochem. J. 1921 15 629-635) .- In 0.5% agar ammonium potassium sodium and magnesium sulphates diffuse almost as fast as in pure water. In 10% gelatin the rate is decreased by about 25%. The diffusion coefficient of copper sulphate in agar is considerably greater than in water and in ISYO gelatin less than in water but still greater than the values for other sulphatea indicate. The abnormal results of von Fiirth and Bubanovid (A. 1920 ii 94) have not been confirmed. The comparatively small uptake of sulphates by plant tissue is not to be explained on the basis of retarded diffusion through a gel.A General Theory of Solutions of Electrolytes. JNANENDRA CHANDRA GHOSH (2. physikal. Chem. 1921 98 211-238).-A theoretical paper in which the author develops a new theory of electrolyte solutions on the basis (i) that in solutions of strong electrolytes only ions exist and (ii) in solutions of weak electrolytes or those of medium strength there exists an equilibrium between a non-polar form (non-electrolyte) and a polar form (which behaves as a strong electrolyte). This hypothesis is examined in connexion with the data obtained in recent years on electrical conductivity activity coefficients conductivity in non-aqueous solvents influence of salts on solubility relations absorption of light by salt solutions and the relation between osmotic pressure and activity coefficients.Theory of Strong Electrolytes. H. KALLMB" (2. physihl. Chern. 1921 98 433437).-A number of criticisms of GhosPs G. B. J. l?. S.ii. 126 SBSTRACTS O F CHEMICAL PAPERS. hypothesis of solutions of electrolytes (T. 1918 113 449 627 707 and preceding abstract) are put forward. GEORGE PUCHER and WILLIAM 91. DEIXN ( J . Arne;.. . CY~enz. Xoc. 1921 43 1753- 1758; cf. A. 1917 ii 445).-The solubility of forty-five organic substances has been determiiied a t 20-25" in ethyl alcohol quinoline and eyuimolecular mixtures of the two solvents. In some cases the solubility in the mixed solvent lies either above or below that in the individual solvents; this is most marked in the case of carbamide " saccharin," p-nitrophenol acetanilide resor- cinol piperine cinnamic acid and chloral hydrate and in all these cases compound formation is indicated.The solubility of carb- amide " saccharin," brucine and o-nitrophenol in a series of mixtures of alcohol a i d quinoline has been determined a t 2 5 O and the solubility G€ lactose a t 1" and 25" and raffinose at 25" in a series of mixtures of water and pyridine has also been determined. It is shown that the solubility of carbamide decreases quite regularly as the concentration of quinoline increases but a t 60% quinoline a break occurs and thc compound of one molecule of quinoline and three molecules of carbamide is formed m. p. 154". Compound formation is indicated in the case of " saccha,rin," brucine lactose and raffinose but no definite compound was isolated. Compound Formation and Viscosity in Solutions of the Types Acid-Ester Acid-Ketone and Acid-Acid.JAMES KENDALL and ELIZABETH BRAKELEY ( J . Anzer. Chem. SOC. 1921 43 1826-1834; cf. Kendall and Gross this vol. ii 32 33).- The viscosity-composition curves a t 25" have been determined for the systems trichloroacetic acid-ethyl acetate acet'ic acid- ethyl acetate trichloroacetic acid-ethyl benzoate acetic acid- ethyl benzoate trichloroacetic acid-acetone acetic acid-acetone trichloroacetic acid-acetophenone acetic acid-acetophenone and trichloroacetic acid-acetic acid. The results obtained indicate extensive compound formation in solutions of the esters and ketones with a strong acid (trichloroacetic). The same substances with a weak acid (acetic) give viscosity curves which are much less abnormal although compound formation is still evident.The curve for the system acetic acid-trichloroacetic acid exhibits con- siderable compound formation and an examination of the results of previous workers on systems of the types acid-acid and acid-base shows that this behaviour is general except when the components are of similar acidic strength. The rules formulated in previous papers relating to the extent of compound formation with diversity in character of the components are confirmed by the present work. Compound Formation and Conductivity in Systems of the Types Formic Acid-Metal Formate and Sulphuric Acid- Metal Sulphate. JAMES KENDALL HOWARD ADLER and ARTHUR W.DAVIDSON ( J . Amer. Chem. Soc. 1921,43 1846-1853; bf . preceding abstract).-Electrical conductivity determinations J. F. S. Solubilities in Mixtures 01 Two Solvents. J. F. S . J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 127 have been made of solutions of various concentrations of barium magnesium and lead formates in anhydrous formic acid at 25" aiid of solutions of sodium barium calcium magnesium zinc lead and silver sulphat,es in anhydrous sulphuric acid. I n this case the solutions contained 0.04 equivalent of solid sulphate. Comparing the results for the formates with those obtained for other formates in formic acid by Schlesinger (&4. 1919 ii 91; 1920 ii 72 73) it is shown that a definite parallelism exists between the degree of ionisation and the extent of compound formation.I n the case of the sulphates however the uncertainty of the correction to be applied for thc solvent is so great as to obscure the results. Vari- ations in compound formation solubility and ionisation in systems of the general type HX-RX are all more extreme the weaker the acidic radicle X . Hydroxides in aqueous solution differ more widely than formates in formic acid and these are more diverse than sulphates in sdphuric acid solution. The Photography of Opaque Crystals. 119. FRANQOIS and CH. LORMAND (Bull. SOC. chim. 1921 [iv] 29 1056-1059).-The application of the apparatus previously described for the photo- graphy of transparent crystals (cf. A. 1921 ii 626) to the photo- graphy of opaque crystals is given in detail.Stereoscopic Photography of Crydals. M. PRANQON and CH. LORMAND (Bull. SOC. chim. 1921 [iv] 29 1059-1063).-For this purpose a microscope the tube of which can be inclined suc- cessively t o the left and right is used. It is fitted with the apparatus previously described for t'he photomicrography of crystals (cf. A 1921 ii 626 and preceding abstract). A photograph is taken with the tube inclined to the Ieft and then one with it inclined equally to the right. The examination of the two photographs in a stereo- scope gives a stereoscopic picture of the crystals in relief. Ionic Properties and Crystallo-chemical Relationships. I. The Properties of the Ions which appear in Crystals. H. GRIMM (2. physikal. Chem. 1921 98 353-394).-,4 theoretical paper in which it is shown that the electrostatic action of the ions in crystals is due to the following ionic properties (i) the charge of the ions (ii) the radius of the ions (iii) the structure of the ions particularly the surface and number of exterior electrons.The ions are divided into five principal groups depending on the number of exterior electrons. (i) Ions of the helium type (2 exterior electrons) (ii) ions of the Ne A Kr Xe and emanation type (8 ex- terior electrons) (iii) ions of the Cu+ Ag+ Au+ type (probably with 18 exterior electrons) (iv) ions of the Te+ and PbT+ type (v) ions of the type Mn++ Fe++ CO++ Ni++ (transition ions). It is shown from many compounds and elements that the expression $A-$Ke>.$xe-+Kr > +Kr- $A holds for many physical properties where $ is the numerical value of the property and the index is that of the inactive gas the structure of which comes nearest to that of the ion concerned.This inequality is due to an analogous inequality of the ionic radii. The ionic radii of 0- S- Se- Te-; AIg++ Cat+ Sr++ Ba++ have been calculated and that J. F. S. W. G. W. G.ii. 128 ABSTRACTS OF CHEMICAL PAPERS. of Cs+ has been approximated. The series order of the other ionic radii has been deduced from the molecular volumes of iso- morphous compounds in which the interchangeable ions have the same number of exterior electrons. Ions with different structures and different exterior sheaths show a similar electrostatic action when the difference in the ionic radius compensates the other properties. J. F.S. Structure of Organic Crystals. SIR W. H. BRAW (Proc. Physical Soc. 1921 34 33-50).-The author has determined the X-ray spectra of naphthalene a-naphthylamine benzoic acid acenaphthene p-naphthol and a-naphthol by the powder method. To interpret the results he has made the assumption that the benzene and naphthalene rings are actual structures having definite size and form and that they are built as a whole into the organic substances in which they occur. It is shown from crystallographic and other data that this hypothesis is an extremely probable one and it leads to results which are in excellent agreement with crystallographic data. It is shown that the unit cell of naphthalene contains two molecules and has a mass of 213 A.U. where 1 &U.= 10-24 grams the linear dimensions of the cell are a=8-34 b=6.05 and c=8.69 B.U.Two molecules of anthracene occupy the unit cell and this has the linear dimensions a=8.7 b=6*1 and c = l l . 6 A.U. The unit cell of acenaphthene contains four molecules and has linear dimensions 8.32 14.15 and 7.26 A.U. respectively whilst a-naphthol has a unit cell which also contains four molecules and has linear dimensions a=13*1 b=4*9 and c=13.4 A.U. ; the same number of molecules occupy the unit cell of p-naphthol and here the linear dimensions are a=5.85 b=4.28 and c=8.7 A.U. The unit cell of a-naphthylamine also contains four molecules and has the dimensions a=8.62 b=14.08 and c=7*04 A.U. Benzoic acid has a wide spacing between the planes the unit cell contains four molecules and has the dimensions a=5.44 b=5.18 and c=21*8 B.U.I n a note the author stated " It is convenient in this work to extend the Angstrom system of units so that an A.U. of area is cm.2 of volume ~111.~ and of mass 10-24 grams." Romtgen Spectroscopic Investigation of Organic Com- pounds. K. BECKER and W. JANCKE (2 physikab. Ghem. 1921,99,242-266,267-.274).-1n the first part an account is given of the X-ray examination of the structure of a number of organic substances. The substances were examined in the form of compressed pastilles by a method which is a combination of that due to Bragg and Debye-Scherrer. In the case of indigotin it is found that the unit cell is an hexagonal parallelopiped with a rhombus as base of edge 19.55 A.U. and height 11.80 A.U. This contains 12 indigotin molecules.The figures refer to indigotin which has been subjected to a pressure of 4000-5000 atoms. Indi- gotin which has not been so compressed has a unit crystal cell with the Linear dimensions a=b=20-20 A.U. c= 12.15 B.U. which means that there is a volume contraction of 9.S% the base de- creases 3.2% and the height %9y0. Carbamide has a unit cell J. F. S. I. and 11.GENEIAAL AND PHYSICAL CHERIISTRY. ii. 129 of dimensions a=b=8.75 A.U. c=7-24 A.U. and contains 8 mole- cules. The unit cell of succinic acid contains 2 molecules and has dimensions a=5.00 A.U. b=8.20 A.U. c=5-40 A.U. p=94.7O0. Compression reduces all values the c value relatively most the values being volume 10*3y0 a 2.2y0 b 4-8% and c 5.4%. Measure- ments are recorded for quinol quinone anthraquinone anthracene naphthalene phenanthrene resorcinol phthalic anhydride phthalic acid cinnamic acid (trans) p-phenylpropionic acid azobenzene hydrazobenzene lithium oxalate maleic acid succinic acid maleic acid d- and I-tartaric acids pentaerythritol a-methylglucoside and acetylenedicarboxylic acid.The results show that the number of molecules in the unit crystal cell is always greater than one and is not the same for nearly related substances such as maleic acid and succinic acid. I n the second paper the results of X-ray examin- ation of a large number of aliphatic acids are given. The results are arranged in four groups. I. Acids with an odd number of carbon atoms formic propionic Valerie heptoic nonoic undecoic. 11. Acids with an even number of carbon atoms acetic butyric octoic lauric myristic palmitic stearic (also aa’- distearin). 111.Isomeric acids isobutyric isovaleric trimethylacetic. IV. Unsaturated acids crotonic undecenoic oleic and elaidic. I n many cases the acids were measured as their lithium salts. It is shown in the case of the even-number saturated acids apart from the first two members that they possess an hexagon symmetry with 72 molecules in the unit crystal or possibly rhombohedra1 with 24 molecules; the uneven-number acids are tetragonal with 24 or 48 molecules in the unit cell. There is no fundamental difference between the free acids and the lithium salts. J. F. S. Mixtures of Anisotropic Liquids and the Identity of Grandjean’s Stratified Liquids with Liquids of the Azoxy- phenetole Type.G. FRIEDEL and L. ROYER (Compt. rend. 1921 173 1320-1322; cf. Grandjean A. 1921 ii 91).-In the case of mixtures of substauces capable of furnishing anisotropic liquids the two phases the conic and thread-like (liquides a coniques et liquides A fils) are perfectly distinct and separated from one another by an absolute discontinuity. Mixtures of Grandjean’s stratified liquids with other anisotropic liquids always show an absolute discontinuity between the stratified liquid and the conic phase. On the other hand these mixtures do not show any dis- continuity between the thread-like phase and the stratified liquid of Grandjean. It is suggested therefore that Grandjean’s stratified liquids are only a special aspect of the thread-like liquids of the type of azoxyphenet ole.W. G. Some Fundamental Conceptions of Colloidal Chemistry. RICHARD ZSIGNONDY (2. physikaI. Chem. 1921 98 14-37).- A theoretical paper in which the nature of matter in the col- loidal condition is considered. The views put forward by Niigeli (“ Garung,” Munich 1879) on the nature of micell= are considered and it is shown that in general these views are in keeping with VOL. CXXII. ii. 5ii. 130 ABSTRACTS OF CHEMICAL PBPERS. experimental data. The conceptions to be generally adopted are expressed as follows by micellae in its broadest sense is to be understood a molecular complex of the dispersed material which is not permeated by the dispersion medium. I n the narrower sense micellae are crystalline ultramicroscopic particles of the dispersed material.Micellar complexes are formed by the association of micellq and are ultramicroscopic particles generally but in isolated cases may be microscopic. According to the form of the association micellar complexes form on the one hand microscopic or ultramicroscopic particles which are permeated by the dispersion medium or on the other ultramicroscopic or microscopic swelling crystals. J. F. S. An Interesting Colloid Gel. Ross AIKEN GORTNER and WALTER F. HOFFMAN ( J . Amer. Chem. SOC. 1921 43 2199- 2202).-Dibenzoylcystine is insoluble in water and in the crystalline state has no hydrophilic properties but it can give rise to rigid gels which do not contain more than 0.2% of dibenzoyl-I-cystine. The 0.2% gel is prepared by dissolving 0.2 gram of dibenzoyl-Z-cystine in 5 C.C.of 95% alcohol. The solution is heated and water added to make the solution up to 100 C.C. After cooling for two to three hours .the solution sets to a gel comparable with that of a 5% gelatin gel. The gel is transparent but after several days opaque nuclei are formed due to crystallisation which is accompanied by syneresis and after several weeks most of the dibenzoyl-I-cystine has separated in definite crystals. On applying strong suction the liquid may be drained from the gel thus showing the coarse dis- persion. The gel has a fibrillar structure. J. I?. S. Coagulation of Colloidal Solutions of Arsenious Sulphide by Electrolytes. E. F. BURTON and E. D. MACINNES ( J . Physical Chem. 1921 25 517-525).-The coagulation of solutions of arsenic sulphide sols of concentrations 0.027 gram per C.C. to 0-00337 gram per C.C.by means of potassium lithium magnesium barium aluminium and zirconium chlorides lanthanum sulphate and cerium nitrate of various concentrations has been investigated. It is shown in the case of aluminium chloride that the volume of the electrolyte required for coagulation of a given amount of the dis- perse phase varies inversely as the concentration of the electrolyte solution provided the final concentration of the colloid is kept constant. For univalent ions it is shown that the concentration of ion necessary to produce coagulation increases with decreasing concentration of the colloid whilst for bivalent ions the concen- tration of ion required to produce coagulation is almost constant and independent of the concentration of the colloid.With tervalent ions the concentration of ion required to produce coagulation varies almost direetly with the concentration of the colloid whilst quadri- valent ions necessary for coagulation decrease much more rapidly than the concentration of the colloid. These results are in keeping with earlier results of Burton and Bishop (A. 1921 ii 176). It is also shown that the coagulation curve for barium chloride showsGENERAL AND PHYSICAL CHEMISTRY. ii. 132 a tendency to resemble the curve for tervalent ions as given by aluminium chloride whilst the curve for the quadrivalent zirconium ion differs from that of the ceric ion which is similar to that for tervalent ions. J. 3'. S. Acidity and Basicity. RUDOLF KELLER (2.physikal. Chem. 1921 98 338-351).-A theoretical paper in which the terms acidity and basicity are considered. It is shown for the determin- ation of the acidity of a combination solute-solvent or the sense of the electric charge not only the inner chemical constitution of the dissolved substance is to be considered but also the chemical constitution of the solvent which may in the case of substances which are nearly amphoteric be determinative. Further the difference in the dielectric constants of the solvent and solute must be considered ; this quantity makes its influence noticeable in the case of amphoteric non-ionised and associated solutes. The so-called basic dyes in aqueous solution usually migrate toward the anode that is they are acid according to the ruling terminology; this is particularly so in the case of the slightly dispersed and non- dissociated colour colloids; the so-called acid dyes are for the greater part basic or amphoteric.Certain acid dyes such as picric acid Martius-yellow aurantia are really acid that is negative and wander to the anode. The capillary rule of Fichter-Sahlbom is generally correctly expressed in the literature but incorrectly defined since it places the dyes in the incorrect position in the electro-polarity series. All the experimental capillarity experi- ments show that immediately on dipping the paper strips the neutral and positive dyes rise with the solvent. I n this correct form the rule holds not only for colloids but also for ion- dispersoids. Gobbelsroder (" Kapillaranalyse," Dresden 1910) has actually found the strongest acids below in the anode region.The strongest acids and bases such as hydrochloric and sulphuric acids and potassium hydroxide in suitable solvents migrate in directions which are opposed to their nature. Concentration cells may be .built up in which the strongest acids behave as bases. J. F. S. Homogeneity and Dispersity. WA. OSTWALD (2. physikal. Chem. 1921 99 155-159).-A theoretical paper in which the conception specific surface is investigated on the basis of the phase rule. J. F. S. Reactions in Heterogeneous Systems. The Systems K2CO3JBaSO4-K2SO4~BaCO3 ; K,CO CaC,04-K2C,04~CaC03 SALLINGER (2. physikal. Chem. 1921 98 103-150).-The systems named in the title have been experimentally investigated. By the addition by barium chloride solution to an excess of a mixture of potassium carbonate and potassium sulphate solution the relation in which barium divides itself between the carbonate and the sulphate ions has been approximately determined. This ratio [CO,l] [SOa"] is termed the preoipitation equilibrium.I n the and M,Cr04~AgI0,-KI03~AgCr0,. I . RAMANN and H. 5 - 2ii. 132 ABSTRACTS OF CHEMICAL PAPERS. case of the addition of silver nitrate solution to an excess of the mixed solutions of potassium iodate and chromate the original equilibrium partition of the silver takes place according to the anion ratio [IO,’] [Cr04”/2] as in the previous case but the two equilibria differ to an extraordinary degree in stability. Whilst the first can be approximately fixed by the rapid addition of alcohol the second can only be fixed by a special experimental procedurc.I n the system xK2CO,+yK,C,O,+xCaC1,(x <x+y) the precipi- tation equilibrium could not be fixed by the addition of alcohol. The precipitation equilibrium in general is labile inasmuch as immediately after the precipitation a reaction is set up which brings about a change in the relationship of the salts in the solid phase and leads to the formation of one of the salts (solution equilibrium). The solution equilibrium has been determined for various concentrations for the system K C0,I BaS04-K,S041BaC03 ; for the system K,CO,I CaC,04-K2C,0~CaC03 a t various total potassium salt concentrations and various temperatures and for the system K,Cr0,(AgI03-I~I0,~Ag,Cr0 at various total salt con- centrations and one temperature (20’).I n the system K,CO,I BaS0,-K,SO,IBaCO the partition relationship K,CO,JK,SO shows a marked dependence on the total salt concentration. No measurements were made on the temperature influence on this ratio. I n the system K,C0,~CaC,04-K,C,0,~CaC0 the partition relationship K,CO,IK,C,O is but slightly influenced by the total salt concentration but very strongly influenced by temperature. The ratio K,CQ31K,C20 is shown to be a strict linear function of the temperature. The data obtained for the systems investigated and those obtained by Knupffer (A. 1898 ii 420) for the system KCNSITlCl-KClITlCNS and by Noyes and Kohr (A. 1903 ii 201) for the system KOHIAgCl-KClIAgOH have been examined by means of the formula put forward by Nernst and Noyes (A 1891 ii 142).J. F. S. Studies on Chemical AEnity. XIII. Reaction M n i t y in Systems of Solid Salts. J. N. BRONSTED (2. physikal. Chem. 1921 98 239-243).-1n earlier papers (A. 1920 ii 290 298) a method was described whereby the reaction affinity between very soluble solid salts might be determined. This method does not yield the required results when applied to sparingly soluble salts. In the present paper a method is described for the determination of the reaction affinity in systems of sparingly soluble solid salts. The method has been applied to the reaction [CoCl(NH,),]Br,+ [ COB~(NH,)~]C~ -+ [CoCl(NH,) ,]Cl,+ [ CoBr (NH,) ,]Br2 and consists in determining the solubility of the four cobalt complex salts in mixtures of (i) potassium formate and chloride solution (ii) potass- ium formate and bromide (iii) sodium chlorate and chloride and (iv) sodium chlorate and potassium bromide where the total alkali concentration is 0.5N in each case.Then from the solubility products of the four cobalt complex salts by means of the gas lawa the reaction affinity may be calculated. The results of the experiments lead to the value d,>=621 cal. for T=273’ a valueOFlNERAL AND PHYSICAL CHEMISTRY. ii. 133 which is probably accurate to 1%. The system is characterised by the fact that the lighter ions are combined with t,he lighter ions and the heavier ions with the heavier. J. F. S. The Velocity of Decomposition of High Explosives in a Vacuum. 111. Mercuric Fulminate. R,OBERT CROSBIE FARMER (T.1922 121 174-187). Sensitiveness of Very Sensitive Explosives. J. EGGERT (2. Elektrochem. 1921 27 547-558).-The sensitiveness of a number of explosives including the iodides of nitrogen has been experimentally investigated. The results show that the inter- molecular decomposition of nitrogen iodide takes place according to the equation 8NH,NI,=5N,+GNH,I+91 whether the decom- position takes place in the dark or in light or is occasioned by detonation. Nitrogen iodide is not sensitive to shock and many effects which were previously attributed to detonation are now shown to be secondary mechanical effects. The sensitiveness of nitrogen iodide and silver amide is not materially changed by lowering the temperature to - 190". Gradual isothermal increase of pressure to 5000 afm.brings about a decomposition in 70% of the cases of nitrogen iodide or silver amide but all othcr explosives examined are unchanged by this treatment. An attempt is made to find an explanation of Ohe sensitiveness of explosives ; since earlier experi- ments have shown that the mechanical effects are not to be explained as secondary temperature effects there only remains the possibility that local increases of pressure occur with all mechanical influences and these are t o be regarded as causing the detonation. This view is supported by the present experiments on the behaviour of the sensitiveness with increase of pressure. A consideration of the processes occurring during the decomposition of explosives from the point of view of Herzfeld's theory of velocity of chemical reaction leads to a possible explanation of some of the properties of these Substances.I n this connexion the primary generally very simple unimolecular decomposition of the explosive which depends on the persistence of the molecule alone is to be differ- entiated from the accompanying at. least bimolecular reaction due to the collision between the products of reaction of the primary process. If in the primary reaction products are formed which possess more energy and a greater persistence than the original substances or if following on the primary process other processes which are subjected to several negative accelerations occur then there will be no marked tendency to detonation. But if on the other hand the primary reaction leads to the stable end products of the reaction or if these products undergo other reactions with no retardations or a t most only one retardation then the explosive is one which has a high sensitiveness and a great tendency to detonation.Pressure is the factor which removes the retardation t o the reactions since it causes the atoms molecules and atomic groupings which have affinities for one anobher to come closer together. J. I?. S.ii. 134 ABSTRACTS OF CHEMICAL PAPERS. The Autoracemisation of Potassium Chromioxalate. ERIC KEIGHTLEY RIDEAL and WILLIAM THOMAS (T. 1922 121 196- 202). Neutral Salt Action at Higher Salt Concentrations ; the Velocity of Hydrolysis of Ethyl Acetate and the Hydrogen-ion Activity of the Catalyst. GOSTA AKERLOF (2. physilcal. Chena. 1921 98 260-292).-The velocity of hydrolysis of ethyl acetate by 0~~5N-solutions of hydrochloric sulphuric and nitric acid a t 25" has been determined in the presence of various concentrations of the chlorides of ammonium potassium sodium magnesium calcium and barium the nitrates of ammonium potassium sodium magnesium and calcium and the sulphates of ammonium potassium sodium and magnesium.The hydrogen- ion activity of the catalyst in the various reaction mixtures has been determined by means of E.H.P. measurements. An attempt is made to ascertain the cause of the neutral salt action on the velocity of hydrolysis a t constant acid concentration by combining the velocity measurements with the hydrogen-ion activity. A relationship between these two quantities is furnished by t'he formula K=Ca .f(n);/& in which K is the reaction velocity n the acid titre and a the hydrogen-ion activity.The formula holds for all concentrations of catalyst and is not influenced by the nature or concentration of the added salt as far as the present experiments go. This formula is probably also true for the inversion of sucrose and allied reactions. The foregoing shows that the hypothesis o€ the catalytic activity of the non-ionised molecule is incorrect. The salt molecules have no activity of their own but they are the cause of the change of activity of the catalyst. Exactly how the neutral salt changes the activity of the catalyst is not known with certainty but the most probable hypothesis is tlhat the water sheath of the hydrogen ion is changed by the addition of neutral salts.The concentration of the hydrogen ion remains constant whilst the activity changes. According to this view the hydration numbers do not represent definite quantities but the ions control all the water molecules in the solution. The various neutral salt actions are controlled by the various forces with which the different ions attract the water molecules. J. F. S. Velocity of Hydrolysis of Acetals. ANTON SKRABAL and ANTON SCHIFFRER (2. physikal. Ch,em. 1921 99 290-313).-The velocity of hydrolysis of methylene dimethyl ether methylene diethyl ether ethylidene diethyl ether methylene diacetate and ethylidene diacetate has been investigated. The reactions were carried out with hydrochloric acid of various concentrations (0.001-0.3N) and also in alkaline solution.It is shown that the measured velocity constants represent the velocity of hydrolysis of the first ether group; the removal of the second group is much more rapid and is regarded as a water hydrolysis. The velocity constants vary very much for the different casm thus for the acid hydrolysis the value of Ic is 70,000 for methylene diethylGENERAL AND PHYSICAL CHEMISTRY. ii. 135; ether whilst for ethylidene diacetate it is 0.00650 whilst in the case of alkaline hydrolysis the value of E is 1,100 for methylene diacetate and 96 for ethylidene diacetate. In the case of the hydrolysis of esters it is shown that the velocity depends largely on the nature of the acid but very little on the nature of the alcohol. These rules are established from the published data of a number of aut h ors .Velocity of Hydrolysis of Sucrose. R. H. CLARK (J. Arner. Chem. Xoc. 1921 43 1759-1764).-The velocity of hydrolysis of sucrose by hydrochloric hydrobromic sulphuric or nitric acid has been determined a t 25". The experiments were effected in the presence of acids of varying concentration and in the presence of potassium nitrate and dextrose. It is shown that the addition of a neutral substance to keep the concentration of the water constant while varying the concentration of the acid has no appreciable effect in producing a numerical proportionality between the quantity of hydrogen ions present and the inversion velocity of sucrose. The increase in the velocity of hydrolysis of sucrose produced by a strong acid in the presence of a neutral salt of that acid over the velocity produced by the acid alone can only t o a small extent be attributed to the fact that the volume of the reaction is reduced by the presence of the salt.On the assumption that both the dissociated and undissociated forms of an acid are catalytically act'ive in sucrose inversion the values of Ki for the hydrogen ion from hydrochloric hydrobromic and nitric acids have the same value (Ki=0.234) ; the corresponding value for sulphuric acid is considerably lower (Ki=O-144). Affinity Dimensions of Weak Acids and Bases in Alcoholic Solution and the Alcoholysis of their Salts. HEINRICH GOLDSCHMIDT CARL GORBITZ HAAEON HOUGEN and KRZSTIAN PAHLE (2. physilcal. Chem. 1921 99 ll&l54).-The theory of the alcoholysis of salts of weak acids with bases of the aniline type in anhydrous alcohol and in alcohol containing water is developed.A method of determining the degree of alcoholysis based on electrical conductivity measurements is described. The electrical conduc- tivity of a series of sodium aniline and ammonium salts in pure and in aqueous alcohol has been determined. The affinity dimen- sion of several organic acids in alcohol solution has been deter- mined. The alcoholytic constant of eleven aniline salts has been measured and from the results the affinity constant Kg corre- sponding with the equilibrium (Aniline x H')/Aniline ion has been calculated. The same quantity has been determined for the three toluidines and mono- and di-methyl anilines. The influence of water and the alcoholytic constants has been investigated.J. F. S. J. F. S. J. F. S. The Rate of Solution of Iron in Dilute Sulphuric Acid both when Stationary and under Rotation. JOHN ALBERT NEWTON FRIEND and JOHN HORACE DENNETT (T. 1922 121 4 1 4 4 ) .ii. 136 ABSTRACTS OF CHEMICAL PAPERS. Theory of Catalysis in Homogeneous Gas Reactions. KARL F. HERZFELD (Z. physilcal. Chem. 1921,9€?,161-174).-A theoretical paper in which an attempt is made to answer the question " Why does a reaction proceed more rapidly through an intermediate product than by the direct action? " It is shown that since a t equal concentration the slowest of all the partial reactions is deter- minative of the velocity of the whole process this slowest reaction must proceed more rapidly than the original reaction when catalysis occurs.After a short review of the previously published theoretical work on gas reactions the author considers such reactions in a way which assumes the existence of a few free atoms. Then for catalysis i t is necessary that a t not too small concentrations 01 the catalyst the heat of activation of the intermediate product (that is practically its heat of formation from atoms) is markedly smaller than that of the starting material ; in the best case about one-half. This gives then an upper limit for the acceleration which at not too high concentrations may be reached by a given catalyst. Examples on which to test the hypothesis are not known. J. P. S. Catalytic Oxidation of Carbon Monoxide. T. K. ROGERS C. S.PIGGOT W. H. BAHLKE and J. M. JENNINGS ( J . Amer. Chem. Xoc. 1921 43 1973-1982).-The present work was undertaken with the object of finding a catalyst which will completely oxidise carbon monoxide a t ordinary temperatures. A number of such catalysts have been prepared which cause rapid and complete oxidation. The chief of the catalysts obtained is a specially pre- pared manganese dioxide on which is precipitated the oxide of silver or copper or both. The silver or copper is best precipitated as the carbonate and subsequently hydrolysed to the hydroxide. The presence of wat,er vapour limits the life of these catalysts. The decomposition temperature of silver oxide when simultaneously precipitated with calcium hydroxide is considerably lower than that of silver oxide alone.J. 3'. S. Catalytic Oxidation of Carbon Monoxide at Ordinary Temperatures. DAVID R. MERRILL and CHARLES C. SCALIONE ( J . Amer. Chern. Soc. 1921,43,1982-2002).-A number of catalysts for use in protective masks against carbon monoxide are described. The most successful are mixtures containing manganese dioxide and basic copper carbonate and manganese dioxide copper oxide cobaltic oxide and silver oxide respectively. These mixtures oxidise carbon monoxide rapidly and at ordinary temperatures and when protected by a drying agent such as calcium chloride are suitable for use in protective masks against carbon monoxide of all concentrations below those in which an oxygen helmet would be necessary. The factors influencing activity such as the con- stituents of the mixtures the conditions of precipitation the mechanical treatment of the precipitate and method of drying are discussed and a description is given of the efficiency of the mixtures under various conditions. J.F. S.GENERAL rWD PHYSICAL CHEMISTRY. ii. 137 Oxidation Catalysis. 11. L. KARCZAG (Bioclzern. Z. 1921 119 16-22).-Experiments with dyes at high dilutions show that the ferrous ion catalyses oxidation with hydrogen peroxide much faster than the ferric ion. The order of mixing is of influence the controlling factor being whether the ferrous ion is fist oxidised to ferric or not. A. D. FOKKER (Arch. NLerZand 1921 5 [iii~] 193-242).-A mathe- matical paper in which it is shown that the application of the electronic theory to the mutual actions of the electrons inside the atom gives results which are in accordance with experimental observations.J. F. S. MAURICE COPISAROW ( J . Amer. Chem. Soc. 1921 43 1870-1888).-Allotropy is defined as the capacity of an element to exist in forms differing in the mode of their intra- molecular linking. It is therefore a function of the valency but it does not imply isomerism or polymerism since allotropes need not contain the same or a multiple number of atoms in their respec- tive molecules. Thenumber of possible forms in which an element can exist on this basis is indicated for the elements of all valencies. It is theoretically possible for an element t o have in certain cases more than one molecular form corresponding with each mode of linking. Regarding allotropes as the most chemically and physically distinct forms of an element i t follows that several molecular forms each containing a different number of atoms but all having the power of free rotation will differ among themselves t o a less extent than when compared with a molecular structure of the same element in which all atoms are rigidly fixed.Thus it follows that valency and the saturation or fixation of atoms and not the actual number of atoms play the predominant part in the deter- mination of allotropes. In this light allotropy becomes the capacity of an element to exist in forms differing in the mode of their intra- molecular linking. Molecular forms differing in the distribution of their intramolecular linking and in thc number of atoms but all belonging to one type of linking can be termed allotropoids.The allotropy of carbon phosphorus iron and nickel are coilsidered from the point of view of the hypothesis. Types of Valency. IRVING LANGMUIR (Science 1921 54 59-67; cf. ibid. 1921 53 290; J . Ind. Eng. Chem. 1920 12 386 and A. 1919 ii 328; also Rydberg A. 1915 ii 94).-Recog- nition of three distinct types of valency (a) positive valency (the number of electrons an atom can give up) ( 6 ) negative valency (the number of electrons an atom can take up) and (c) co-valency (the number of pairs of electrons an atom can share with its neigh- bours) as well as the numerical values for most of the elements of each type are shown by a simpler method than that hitherto employed to be derived from certain postulates regarding the struc- ture of atoms and the relationships between the different types of valency are thereby further clarified.On the basis of the H. K. Electronic Theory of the Interior of the Atom. Theory of Allotropy. J. F'. S. 5'ii. 138 ABSTRACTS OF CHEMICAL PAPERS. Rutherford atom only three postulates consistent with those previously proposed are necessary (a) The electrons in atoms tend to surround the nucleus in successive layers containing 2 8 8 18 18 and 32 electrons respectively (the extra electrons if any remaining in the outside layer as an incomplete layer or “ sheath ”). ( b ) Two atoms may be coupled together by one or more duplets (stable pairs of electrons forming the first complete layers) held in common by the completed sheaths of the atoms. A group of neutral atoms interacting by transfer of electrons gives rise to the conception of electrovalency including positive and negative valency differing only in algebraic sign whilst interaction by the sharing of duplets corresponds with co-valency.It is shown that the sum of the electrovalencies and co-valencies for all the atoms in any complete compound is zero a complete compound being defined as one in which all the atoms possess complete layers of electrons. (c) The residual charge on each atom and on each group of atoms tends to a minimum. The term “ residual charge ” is employed to express the total charge of an atom or aggregate of proximate atoms regardless of sign. It is pointed out however that the first and third postulates are often in conflict and that in such cases the tendency of the first may prevail against that of the third.Chemical compouirds are theref ore classified according to the types of valency exhibited by their atoms as follows (1) complete compounds including (a) compounds without co-valency such as certain simple metallic salts volatile halogen compounds silicates and most minerals and ( b ) compounds without electropositive atoms such as organic compounds ; (2) incomplete compounds including metallic substances and compounds such as zinc oxide ferroso-f erric oxide lead sulphide and cupric oxide which contain both electropositive and electronegative atoms ; (3) exceptional cases including nitrogen carbon monoxide nitric oxide and the cyanogen radicle the structure of which is not accounted for by this theory.These substances may have a single octet structure or possibly a triple bond structure. Other exceptions are boron hydride and certain other compounds f orrning double molecules. A. A. E. The Expression of the Octet Theory of Valence in Structural Formulae. GRANVILLE A. PERKINS (Philippine J . Xci. 1921,19 1-22).-A system for writing structural formulae is developed based on the octet theory of valency as presented by Langmuir. Electronegative valence the physical interpretation of which is vacancy for one more electron in the outer shell of the atom is represented by a line in the usual way. Electropositive valence on the other hand is variable and its maximum is represented by the total number of electrons in the shell. It cannot be repre- sented by “unsatisfied bonds” as it never causes direct union between atoms and is expressed as follows for example Na’ CaII. The neutral atoms having electronegative valence may satisfy that valence by acquiring an electron that is becomingGENERAL AND PHYSICAL CHEMISTRY. ii. 139 a negative ion; this electron may be obtained from the shell of an atom showing positive valence tendencies and it is then left as a positive ion. These two oppositely charged ions may then form a stable compound by electrostatic attraction. Such a union is termed a salt-forming union and is expressed thus Naf . . . . . Cl- or Ca*+ 0-. On the other hand two atoms may be held together by the shell-completing forces of both atoms acting on one or more pairs of electrons which are then shared between them. Each shell thus fills one or more electron vacancies by sharing electrons ‘and thus “ satisfies ’’ one or more “ bonds.’’ This is expressed in the usual way 13-€I H-0-H etc. and is termed a direct union. All valency relations cannot however be expressed in terms of either of the above unions and a special feature of the system is the introduction of the conception of a “borrowing direct union,” for cases in which both the shared electrons are supplied by the same atom. In this case the borrow- ing atom fills two vacancies in its shell and the lending atom neither gains nor loses electrons; but the union is essentially polar since the originally neutral borrowing atom has acquired at least an interest in two negative electrons and therefore becomes a negative pole. This relationship is expressed. thus :>0 oc0,O-S a0 indicating that the 0 atom is bound to S or to 0 by virtue of having its two electron vacancies filled by borrowing an interest in two of the shell electrons of the other oxygen atom in hydrogen peroxide an$ in the sulphur atom of sulphur trioxide. The mode of application of the system to all the known elements is indicated in the original paper. G . P. M. CLAUDE W. BOURLET and WALTER THOMAS (Chem. News 123 336).-The thermos flask can be utilised advantageously in the laboratory in numerous instances where it is desired to maintain substances above the normal temperature as for example in reactions between liquids or liquids and solids a t elevated temperatures such as hot oxidation by permanganate and other similar reactions which are not strongly exothermic. Oil and water emulsions and similar mixtures are conveniently ‘‘ split ” by warming and keeping over- night in a thermos flask and flocculent or colloidal precipitates can be dealt with in a similar manner. In carrying out certain colour tests for example the Halphen reaction and reactions in media which gelatinise or become viscous a t ordinary temperatures a water-bath can with great advantage be replaced by the vacuum flask. 8 0 The Thermos Flask in the Chemical Laboratory. G. F. M. Water Pump. JOHANNES WETZEL (Chem. Ztg. 1921 45 1122).-A water pump of improved efficiency is described; par- ticular attention is directed to the relative diameters of the injector tube and outlet tube and to the central position of the jet as regards the outlet tube. w. P. s. 5”-2

ISSN:0368-1769    

DOI:10.1039/CA9222205097

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

i. 101 Organic Chemistry. Relation between the Molecular Properties and the Capacity for Fixation of Iodine of certain Hydrocarbons. PAUL Wooa (Compt. rend. 1921,173 1471-1473; cf. A. 1921 ii 575) .-Plotting the molecular weights of a homologous series of American oils against the corresponding iodine values reduced pro- portionately to the double linkings as calculated from the mean molecular surface area on water (loc. cit.) a regular curve was obtained given by the equation log INo+K=log 1 2 5 0 ) where IN0 is the iodine value for any molecular weight and 1 x 5 0 the value for a molecular weight fifty units higher and K is a constant equal to 0.0664. This progressive capacity for addition or substitution is apparently due to causes analogous to those responsible for the dissociations which occur in the " cracking " process.Benzene solutions of these oils rapidly undergo oxidation *hen exposed to sunlight and the velocity of oxidation increases with the number of double bonds in the molecule. A General Method for the Preparation of Carbides of Metalloids and the Existence of Carbides of Phosphorus and Arsenic. E. DE MAHLER (Bull. SOC. chim. 1921 [iv] 29 1071-1073).-The chloro-derivative of the metalloid is allowed to react in ethereal solution a t the ordinary temperature with one of Iotsitsch's compounds (cf. A. 1914 i 393) of the type MgICiC-MgI when the carbide of the metalloid is obtained. In this way phos- phorus trichloride gives phosphorus carbide P-C.C- P an amor- phous white compound which is spontaneously inflammable when gently warmed and yields phosphoric anhydride and carbon dioxide.Arsenic chloride gives arsenic carbide AsZC6 a brown amorphous compound which explodes when warmed or gently rubbed arsenic and carbon being liberated. W. G. pic\ b C / W. G. Some Aliphatic Fluorides. F. SWARTS (Bull. SOC. chim. EeZg. 1921 30 (ii) 302-315).-The following are described n-AmyZJluoride a volatile mobile liquid m. p. below -80" b. p. 62.8" d10'5 0.7960 dzo 0*7880 nz 1.35622 n? 1.36183 n; 1.36533. n-Decyl Jluoride a mobile liquid which solidifies in a mixture of alcohol and solid carbon dioxide b. p. about 183.5" d10'2 0.792. isoAmyl Jluoride b. p. 53.5". n-Heptyl Jluoride m. p. -73" b. p. 119"/755 mm. dZ1 0.8029 7 ~ ' ~ 1-38358 ng'5 1.3855 n:'.? 1.3899 ny'5 1.39358. n-0ctyZ Jluoride b.p. 142*5"/75 mm. d14 0.81200 d21 0.8036 ni4.1 1.3952 n$.l 1.3970 n;P" 1.40175 ny'l 1.43565. Cetyl Jluoride is solid a t the ordinary temperature VOL. CXXII. i. ei. 102 ABSTRACTS OF CHEMICAL PAPERS. b. p. 287*5"/760 mm. 181°/24 mm. d17'5 0,809. sec.-OctyZ fluoride b. D. 139.3". ft is stated that mercury fluoride is preferable to silver fluoride for the preparation of the above several reasons being given. The yield is diminished in each case by the formation of an ethylenic hydrocarbon and hydrogen fluoride ; when silver fluoride is used this may take place in such a way that two molecules of the alkyl haloid containing Cn condense to yield C&Hqn+ ,F ; sometimes this represents the major reaction. The chemical properties of the substances are described; they are in general not so stable as the majority of organic fluorine compounds.The isoalkyl fluorides tend to decompose into ethylenic hydrocarbons and hydrogen fluoride on distillation ; with straight-chain compounds this is not the case. The action of alkali hydroxides in aqueous or alcoholic solution is feeble ; concentrated sulphuric acid reacts in the cold with formation of hydrogen fluoride. The Aliphatic Sulphonamides. I. PERCIVAL WALTER CLUTTERBUCK and JULIUS BEREND COHEN (T. 1922 121 120- 128). ECMUND 0. VON LIPPMANN (Chem. Ztg. 1922 46 4-5).-Historical. ERICH NULLER (2. EEeEtro- chem. 1921 27 563-567; cf. this vol. i log).-A number of alcohols including ethyl alcohol propyl alcohol isobutyl alcohol isopropyl alcohol benzyl-alcohol ethylene glycol glycerol and mannitol in strongly alkaline solution on electrolysis or in the presence of oxidising agents such as potassium ferricyanide or in the presence of colloidal rhodium give rise to hydrogen or hydro- carbons.The reaction is explained by the assumption that in the oxidation of alcohols to aldehydes a metastable intermediate product is formed which in the presence of metals breaks down to hydrogen or hydrocarbons according to the scheme (1) CH,*CH,*OH CH,*CH,*O'+H' and (2) H. J. E. The History of [Ethyl] Alcohol. Dehydroxidation of Alcohols. / CH3*CHO+H-+2H-+H \ CH,O+CH +2CH3+C,H CH,*CH,*O'+P=CH,*CH,*O / CH4 J. F. S. The Influence of Potassium Hydroxide on the Formation of Vinyl Alcohol from Acetaldehyde. WILLIAM LLOYD EVANS and CLOYD D. LOOKER ( J .Amer. Chern. SOC. 1921 43 1925- 1928).-Poleck aAnd Thummel's vinyl oxymercurochloride (A. 1890 112) is obtained when alkaline solutions of acetaldehyde are treated with mercuric chloride the yield of the oxymercurochloride being proportional to the concentration of the alkali present. Thus the production of vinyl alcohol is likewise proportional to the concen- tration of the alkali and since vinyl alcohol is a necessary inter- mediate product in the formation of oxalic acid in the oxidationORGANIC CHEMISTRY. i. 103 of ethyl alcohol and acetaldehyde the yield of oxalic acid must also be proportional to the concentration of the alkali used. A minimum concentration of about 1.40 grams of potassium hydroxide per litre is necessary for the formation of vinyl alcohol a t 25".W. G. Poly-ethers of Trimethylene Glycol. C. A. ROJAHN (Ber. 1921,54 [B] 31 18-3121).-During the purification of trimethylene glycol (this vol. i 105) considerable quantities of residue are obtained in which the presence of poly-ethers of trimethylene glycol was suspected. Attempts to isolate a uniform substance therefrom by fractionation under diminished pressure did not give entirely satisfactory results owing to the continuous formation of resin but the molecular weights of the individual fractions in boiling alcohol pointed to the conclusion that they contained di- to hexa-ethers. Further purification was attempted by conversion of the individual fractions into the corresponding phenylurethanes (which was only successful with the fraction of molecular weight corresponding with the di-ether) by acetylation and subsequent quantitative hydrolysis of the acetates and by fission of the ethers.The diphenylurethane of di-trimethylene glycol ether C2,H2,05N2 crystallises in small colourless needles m. p. 104-105". The fraction b. p. 130-170"/12 mm. yielded di-trimethylene glycol ether diacetate O(CH2*CH2*CH2*OAc) a colourless somewhat viscous liquid b. p. 181-183"/52-54 mm. 265-27O0/atmospheric pressure (slight decomp.) d$:f 1.0864 which was hydrolysed to the corresponding di-ether a colourless syrupy liquid b. p. 155- 160"/15 mm. di;: 1.064. Similarly the fraction b. p. 180- 210"/12 mm. gave the diacetate of tri-trimethylene glycol ether a colourless viscous liquid b. p. 238"/80 mm. d$' 1.0546. Di-trimethylene glycol ether is decomposed by a boiling saturated solution of hydrogen bromide in glacial acetic acid and subsequent treatment of the product with alkali hydroxide solution into tri- methylene glycol which was identified as the di-benzoate needles m.p. 60-61" thus establishing the constitution of the ether. Protracted ebullition of trimethylene glycol under the atmo- spheric pressure leads to the formation of poly-ethers. Derivatives of Acetylenic Erythritol [Hexinene-ccp~[-tetrol] HO*CH,*CIQ( OH)*CI CGH (BH)*CH,*OH. R. LESPIEAU (Compt. rend. 1921 173 1367-1369).-Chloroacetaldehyde reacts with the dimagnesium derivative of acetylene in the presence of ether to give a black viscous mass which when further treated with bromine in chloroform solution gives a product which crystallises after several months.It is a~-dichloro-y6-dibromohexen-~~-dioE CH,Cl*CH( OH)*CBr:CBr*CH(OH)*CH2C1 m. p. 141-142-5". The black viscous mass mentioned above when treated with solid Dotass- H. W. ium hydroxide in ether gives the dioxide yHD CH*CiC*CH<?H2 O- 0 b. p. 87.5-88.5"/10 mm. do 1.417 W- G. e 2i. 104 ABSTRACTS OF CHEMICAL PAPERS. Alkylations. I. Alkylation of Sodium Sulphite. H. BAGGESGAARD-RASMUSSEN and SVEN WERNER (Bull. SOC. chim. 1921 [iv] 29 1073-1087).-A quantitative study of the inter- action of methyl or ethyl iodide and sodium sulphite in 30% methyl alcohol shows that the reaction is essentially bimolecular although the curve is somewhat irregular towards the end. The abnormal progress of the reaction may be explained on the basis that in solution sodium sulphite exists in two tautomeric forms which are in equilibrium NaSO,*ONa SO(ONa) and that only the first undergoes alkylation the atom of sodium attached to sulphur being replaced by the alkyl group.The results indicate that in solution 88% of the sodium sulphite is in the first form and 12% in the second. W. G. Neutralisation of the Affinity of Main and Subsidiary Valencies in Compounds of a Higher Order. 111. J. V. DUBSKY [with P. APTEKMANN] ( J . pr. Chem. 1921 [ii] 103 109- 128; cf. A . 1916 i 541).-Investigation of the behaviour towards pyridine of nickel salts of various substituted xanthic acids shows that the ability of xanthates of the general formula OR*CS*SX to form additive compounds with pyridine is independent of the volume of the radicle R although the stability of the additive product diminishes with the magnitude of R.Unlike the cobalt xanthates previously investigated cobalt amyl benzyl and bornyl xanthates unite with two molecules of pyridine giving additive compounds far less stable than those given by the corresponding nickel salts. It is not found possible to convert either tertiary alcohols such as dimethylethylcarbinol or phenols into the corresponding xanthic acid derivatives (cf . Meyer " Analyse und Konstitutionsermittlung organischer Verbindungen," 3rd ed. 474) but analogous secondary alcohols such as cyclohevanol or borneol readily yield xanthic acid compounds. These results are in accord with those of Bamberger and Lodter (A. 1890 517) who found that 5 6 7 S-tetrahydro- 2-naphthol acts as a true phenol and gives no xanthate whereas the isomeric 1 2 3 4-tetrahydro-2-naphthol behaves as a secon- dary alcohol (cf.Lippmann and Fleissner A. 1888 296). Nickel propyl xanthate Ni(CS,*OPr) forms brown crystals and gives with pyridine the compound C,H140,S4Ni,2C5H,N which separates in pale green crystals and is unstable in the air. Nickel butyl xanthate Ni(CS,*O*CH,Pr) forms brown crystals and gives ZL pale green compound with 2 molecules of pyridine. Nickel amyl xanthate Ni(CS,*O*CH,*CH,Pr) crystallises in brown leaflets with a greenish-yellow lustre and forms a pale green compound with 2 molecules of pyridine. Cobalt amyl xanthate gives an unstable brown compound with 2 molecules of pyridine. Nickel cetyl xanthate Ni(CS,*O*[CH,]15~CH,)2 crystallises in orange-yellow leaflets and forms a very unstable green compound with 2 molecules of pyridine.Cobalt cetyl xanthate forms green crystals. Sodium benzyl xanthate NaCS,*O*CH,Ph and the potassium salt were prepared. Cobalt ben~yl xunthte Co(CS,*O*CH,Ph) forms lustrous black crystals,ORGANIC CHEMISTRY. i. 105 gives a deep green solution in benzene and with 2 molecules of pyridine yields a brown compound which is highly unstable even in an atmosphere of pyridine. Nickel benxyl xanthate forms black crystals and with 2 molecules of pyridine yields a compound which remains unchanged in an atmosphere of pyridine. Potassium cyclo- hexyl xanthate KCS,*O*C,H, is crystalline and the nickel salt Ni(CS,*O*C,H,,) forms brown crystals.Xodiurn bornyl xanthate NaCS,*O*C,,H1 is crystalline ; the nickel salt forms brown crystals and the cobalt salt forms with 2 molecules of pyridine a highly unstable brown crystalline compound. pp'-Dichlorodiethyl Ether. The Oxygen Analogue of Mustard Gas. OLIVER KAMM and JOHN H. WALDO ( J . Amer. Chem. Soc. 1921 43 2223-2227).-pp'-DichEorodiethyl ether b. p. 177-178" (corr.); dg 1.213; n20 1.457 may be prepared by the action of concentrated sulphuric acid on ethylene chlorohydrin. When condensed with aniline it gives 4-phenylmorpholine. When condensed with ethyl malonate the ether gives ethyl tetrahydro- pyran-4 4-dicarboxyhte o<CH~.CH~>C(C02Et)2 CH C H b. p. 260"/740- 745 mm. d3 1,107. which with carbamide in the mesence of T. H. P. sodium ethogide yields tetrahydropyran-4 5-spiro-2 14 6-triketo- hexahydrop yrimidine 0 < :2::2>C< :::::> C:O m.p. 2 18". p p'-Dichlorodiethyl ether inlige its sulphur analogue exerts no deleterious action on the tissues of the animal body. Similarly tetrahydropyran-4 5-spiro-2 4 6-triketohe~ahydropyrirnidine~ al- though closely related in structure to barbital possesses no marked hypnotic properties. W . G. 77'-Dihalogenodipropyl Ethers. OLIVER KAMM and WALTER H. NEWCOMB ( J . Amer. Chem. Soc. 1921 43 2228-2230).- yy'-Dichlorodipropyl ether b. p. 215'1745 mm. ; dj 1.140 was obtained by boiling trimethylene chlorohydrin with sulphuric acid under a reflux condenser. Attempts to prepare trimethylene bromohydrin from trimethylene glycol by the action of hydrobromic acid and sulphuric acid gave a mixture of ay-dibromopropane the required bromohydrin and yy'-dibromodipropyl ether b.p. 128",/19 mm.; dz 1.574. The products can be separated by fractional distillation. Preparation of p-Chloro- and g-Bromo-propionic Acids €rom Trimethylene Glycol. C. A. ROJAHN (Ber. 1921 54 [B] 31 15-3118).-Trimethylene glycol is present in considerable amount in the sweet water concentrates obtained by the fermenta- tion of sugar to glycerol by the method of Connstein and Ludecke particularly when the operation is conducted with insufficient care. It is purified by distillat'ion dilution of the fraction b. p. 170-230" with water and treatment of the hot solution with lead oxide and barium hydroxide in a current of air. After removal of lead and barium by sulphuric acid air is passed through W.G.i. 106 ABSTRACTS OF CHEMICAL PAPERS. the hot solution whereby the bulk of the organic acids are removed and trimethylene glycol b. p. 210" d; 1.0573 is ultimately isolated by repeated distillation finally under diminished pressure. It is treated at the temperature of boiling water with about two-thirds of the calculated quantity of hydrogen chloride and the product is fractionated giving thereby (i) water and dichloropropane (ii) y-chloropropyl alcohol (iii) unchanged trimethylene glycol and (iv) a residue (see this vol. i 103). p-Chloropropyl alcohol is added gradually to nitric acid (30%) a t 0" and the mixture maintained a t below 5" during twenty-four hours after which it is cautiously treated at 30-35" allowed to remain during eight hours and subsequently heated a t 70-75" ; p-chloropropionic acid colourless needles m.p. 37-38" is thus formed in 3 0 4 0 % yield. Trimethylene glycol is converted by boiling hydrobromic acid into a mixture of ay-dibromopropane and y-bromopropyl alcohol. The latter is oxidised by nitric acid to p-bromopropionic acid b. p. 140-142"/45 mm. m. p. 62-63'; the action proceeds less violently than with 7-chloropropyl alcohol. The Mixed Anhydrides of Sulphuric Acid and Carboxylic Acids. 11. rz-Butyrylsulphuric Acid. A. J. VAN PESKI (Rec. trav. chim. 1921 40 736-746; cf. A. 1921 i 302).-n-Butyryl- sulphuric acid C,H,*CO*O*SO,H is formed by the action of sulphur trioxide on n-butyric acid and resembles acetylsulphuric acid in its general properties.When heated it is transformed into a-sulphobutyric acid and a t 70' evolution of carbon dioxide takes place with sharp rise in temperature to about 110" the other product being a-sulphobutyrone. Full experimental details are given as to the preparation of the acid its sodium salt and from the latter of butyric anhydride the preparation of isoamylsulphuric acid phenyl butyrate tribromobutyranilide (long needles m. p. 167*8") tribromobutyrophenol (a pale yellow viscous liquid m. p. 6-9' b. p. 192*8"/16 mm. corr.) are described and also the sulphon- ation of benzene by the acid. CIS Fatty Acids. 11. The Relation of Oleic and Elaidic Acids to their Halogen Additive Products. BEN H . NICOLET ( J . Amer. Chem. Soc. 1921,43 2122-2125; cf. A. 1921 i 390).- Using the anilides of the various acids as means of characterising them it is shown that there is no cis-trans-isomerisation when bromine is added to the double bond and later removed by zinc and alcoholic hydrochloric acid in the case of oleic or elaidic acids.These acids thus differ from linolic acid in this remect. Oleanilide H. W. H. J. E. dibromide has m. p. 67"; elaidanilide dibromide ha; m. p. 88". W. G. The Mechanism of the Oxidation of Drying Oils as 111. SAMUEL COFFEY (T. 1922,121 17-23). The Formation of Substituted Succinic Acids from Esters LUCY HIGCtMBOTHARl and ARTHUR Elucidated by a Study of the True Oxygen Absorption. The Action of Driers. of up-Unsaturated Acids. LAPWORTH (T. 1922,121 49-54).ORGANIC CHEMISTRY. i. 107 Nitromalic Acid.ARTHUR LACHMAN ( J . Amer. Chem. Soc. 1921 43 2084-2091; cf A. 1921 i 303).-NitromaZic acid m. p. 110-112") is readily obtained by adding fuming sulphuric acid to a cooled solution of malic acid in nitric acid (d 1.42). It gives a sodium and a silver salt. When hydrolysed with sodium hydroxide in aqueous solution it yields a mixture of nitric and nitrous acids the percentage of nitrous acid being independent of the temperature the concentration or the presence of an excess of alkali. Similar results were obtained in methyl alcohohc solution except that the amount of nitrous acid obtained was nearly twice that in aqueous solution. When alkali was excluded altogether and a substance such as sulphanilic acid capable of reacting with the nitrous acid as fast as it is formed was present the production of nitrous acid was greatly increased and the rate under these conditions corresponded with a unimolecular reaction. In the hydrolysis of nitric esters two independent processes occur.One is the normal hydrolysis into alcohol or hydroxy-acid and nitric acid and the second is isomerisation to a nitrous ester which subsequently is hydrolysed to an aldehyde or a ketone. Each of these reactions proceeds a t its own rate under given con- ditions. The action of alcohol in increasing the yield of nitrous acid is that it diminishes the rate of the normal hydrolysis of the nitric ester to nitric acid. The constant yield when alkali is employed is a false equilibrium. The real constant is the ratio of the velocities of the two reactions. W. G.Stereoisomeric Ethylthiolsuccinic Acids. PETER FITGER (Ber. 1921 54 [B] 2943-2951).-r-Ethylthiolsuccinic acid CO,H*CH(SEt)*CH,*CO,H small colourless needles m. p. 124- 126" is prepared from ethyl mercaptan sodium bromosuccinate and sodium hydroxide in aqueous solution or by the action of ethyl bromide and sodium hydroxide on sodium thiolsuccinate dissolved in water. The normal salts with the exception of those of silver lead and iron are generally freely soluble in water; the sodium hydrogen potassium hydrogen and barium hydrogen salts crystallise in colourless prisms. Attempts to resolve the racemic acid into its optically active components by means of the phenyl- ethylamines were unsuccessful since a partly racemic salt is the least soluble. On the other hand a partly active d-acid could be obtained by the action of ethyl mercaptan and sodium hydroxide on an aqueous solution of.sodium I-bromosuccinate and from this the pure d-variety could be isolated with the aid of d-phenyl- ethylamine. d-Ethylthiolsuccinic acid m. p. 126-128" forms lustrous aggregates of prisms or needles ; it has [ayi+139*3° in absolute alcohol [a]:+ 149.8" in ethyl acetate [a]:+ 145.0" in acetone [a]E+107.7" in water. Under certain conditions it is possible to isolate the almost pure d-acid by the process described above in relatively good yield and without recourse to d-phenyl- ethylamine. LEthylthioZsuccinic acid is obtained in good yield by the action of ethyl bromide and sodium hydroxide on an aqueouei. 108 ABSTRACTS O F CHEMICAL PAPERS.solution of sodium 1-thiolsuccinate ; it forms aggregates of lustrous needles m. p. 126-128' [a]~-139*3' in absolute alcohol [a]~-l50.0" in ethyl acetate [a]?- 145.1' in acetone [a]$- 108.0" in water. It was not found possible to isolate well-defined salts of the active acids. H. W. Certain Products of the Oxidation of Inactive Ethylthiol- succinic Acid. PETER FITQER (Ber. 1921 54 [B] 2952- 2963 ; cf. preceding abstract) .-Ethylthiolsuccinic acid is oxidised by hydrogen peroxide to ethylsulphoxysuccinic acid CO,H-CH ( SOEt ) *CH,*CO,H which becomes discoloured a t 120' but does not errhibit a definite melting point when more strongly heated. The ferric and silver salts are described but in general the normal salts do not appear to be sharply characterised.The acid is unstable when dissolved in water or ethyl acetate Pnd in boiling solution becomes decom- posed into carbon dioxide ethyl mercaptan diethyl disulphide fumaric acid and p-ethylthiolacrylic acid long colourless slender needles m. p. 83-84". Sodium ethylthiolsuccinate is oxidised by potassium perman- ganate in aqueous solution and in the presence of carbon dioxide to r-ethyZsuZ~honylsuccinic acid long colourless prisms m. p. 167- 168" ; the sodium salt C,H,0,SNa,,2H2O colourless rhombic plates barium salt pointed prisms silver salt (+2H,O) prisms and ferric salt are described. The action of bromine on an aqueous solution of r-ethylthiol- succinic acid appears to lead to the initial formation of ethyl- sulphoxysuccinic acid (which is too unstable to permit its isolation in these circumstances) and then to ethylsulphonylsuccinic acid which can only be prepared in poor yield in this manner.The use of three molecular proportions of bromine on the other hand readily gives a- bromo-a-ethylsulphonylsuccinic acid CO,H*CBr (S 0,Et ) *CH,*CO,H colourless microscopic plates (+H,O) m. p. 83-85' (decomp.) ; the silver ferric and barium (+3H,O) salts are described. The acid readily eliminates carbon dioxide in hot aqueous acidic solution and passes into p-bromo- p-et7Lylsulphonylpropionic acid colourless prisms m. p. 142-143" (decomp.) ; the ferric salt and silver salt needles are described. Ethylthiolsuccinic acid when dissolved in glacial acetic acid reacts vigorously with bromine giving a-bromo- p-ethylthiolmaleic acid CO,H*CBr:C(SEt)*CO,H pale yellow thin plates or flattened prisms m.p. 131" to 141" (decomp.) according to the mode of heating. The barium salt voluminous needles and the anhydride long pale yellow needles m. p. 44-45" are described. Ethylthiolsuccinic acid is extensively decomposed by potassium permanganate in bicarbonate-alkaline solution but the products formed have not yet been identified. A. BENRATH and J. OBERBACH (2. physikd Chem. 1921 98 49$-501).-The H. W. Behaviour of Fehling's Solution in Light.ORGANIC CHEMISTRY. i. 109 authors have been unable to confirm the statement ofjBolin and Linder (A. 1920 ii 144) that when Fehling’s solution contained in glass vessels is exposed to ultra-violet light no reaction occurs. It is found that Fehling’s solution exposed in a glass tube to sun- light is decolorised with the evolution of hydrogen.Illumination of an alkaline solution of potassium sodium tartrate gives no evolution of gas but if cuprous oxide is added hydrogen is vigor- ously evolved; copper turnings and even massive copper have the same action. Fehling’s solution to which copper has been added evolves hydrogen immediately it is exposed to light and the action persists €or some time after the light is removed. The oxidation products of tartaric acid such as dihydroxytartaric acid mesoxalic acid and formic acid when treated with alkali hydroxides and metallic copper evolve hydrogen in light. Mes- oxalic acid has the most pronounced action and the insoluble sodium dihydroxytartrate passes into solution with the evolution of hydrogen.If dihydroxytartaric acid is added to Fehling’s solution it is decolorised more rapidly than if the addition has not been made. In all cases where the reaction was carried out in quartz vessels a thin deposit of copper was found on the walls of the vessel. The reaction probably follows the course the Fehling’s solution decomposes in light forming cuprous oxide and metallic copper and these act catalytically on the tartaric acid producing hydrogen and oxidation products of tartaric acid. Some of the oxidation products are further oxidised in the dark. J. F. S. Dihydroxytartaric Acid. ARTHUR LACHMAN ( J . Amer. Chem. SOC. 1921 43 2091-2097 ; cf. Fenton T. 1898 74 71 ; 1902 81 426) .-Dihydroxytartaric acid considered as a diketone has a structure similar to benzil and when acted on by alkalis behaves like benzil and thus its decomposition is represented by the equations CO,H*CQ*CO*CO,H+H,O=CO,H*CHO+ (CO,H) C02H*CQ*CO*C02H+H20=C02H*C( OH)(CO,H) the carboxytartronic acid losing carbon dioxide and giving tar- tronic acid.It is shown that when sodium dihydroxytartrate is heated at 160° carbon dioxide is evolved and glyoxylic acid and oxalic acid were identified along with tartronic acid in the products of decomposition. In Fenton’s method for the estimation of sodium by precipitation as sodium dihydroxytartrate and subsequent oxidation of this salt with standard permanganate it is necessary to carry out the oxid- ation first in alkaline and then in acid solution in order to obtain consistent results.W. G. Internal or Catalytic Dehydroxidation of Formaldehyde. ERICH MULLER (2. Elelitrochem. 1921 27 558-563).-Alkaline solutions of formaldehyde when treated with oxidising agents such e*i. 110 ABSTRACTS OF CHEMICAL PAPERS. as cuprous oxide cupric oxide silver oxide potassium persulphate hydrogen peroxide or potassium ferricyanide are converted into formic acid with evolution of hydrogen. The same reaction occurs on electrolysis of an alkaline solution of formaldehyde and finally finely divided metals (Cu Ag Pd Pt,) when added to alkaline solutions of formaldehyde bring about a rapid evolution of hydrogen and formation of formic acid. The catalytic change is best shown with colloidal rhodium thus If to 30 C.C. of 15N-sodium hydroxide and 50 C.C. of 20% formaldehyde 20 c.c of colloidal rhodium (0.05 gram) are added a t 25” there is an evolution of 3 litres of hydrogen in two hours.The author explains the electrolytic reaction as follows In solution formaldehyde exists in equi- librium as represented by the equations HCHO+H,O zz HCH(OH) HCHO’(OH)+H’ on the anode the reaction HCH( OH)O’+P=HCH(OH)O takes place ; this substance the author terms an 0-aldehyde and states that it may exist in the metastable condition in formaldehyde solution up to a definite concentration. Above this definite concentration it spontaneously decomposes to give hydrogen and formic acid H*CH(OH)O -+ HC(OH)O+H but a t lower concentrations it is decomposed only by oxidising agents or catalysts. This reaction the author terms “ dehydroxidation.” The course of the reaction with catalysts is represented as follows I n alkaline solution a reaction similar to Cannizzaro’s reaction occurs in two stages (1) 3HCHO+2H20= CH,OH+BHCH(OH)O and in the presence of the catalysts (2) 2HCH( 0K)O =2HC02H+ H,.J . F. S. Alcoholic Fermentation of Formaldehyde by Osmium. ERICH MULLER (Ber. 1921 54 [B] 3214-3216).-An aqueous solution of formaldehyde decomposes in the presence of osmium into carbon dioxide and methyl alcohol. The catalytic activity of the metal diminishes somewhat rapidly. At about 50° and then only to a small extent hydrogen is also evolved. H. W. The Rijle of Mercury Salts in the Catalytic Transformation of Acetylene into Acetaldehyde and a New Commercial Process for the Manufacture of Paracetaldehyde. RICHARD R.VOGT and JULIUS A. NIEUWLAND ( J . Arner. Chem. Soc. 1921 43 207 1-2081) .-In the commercial preparation of acetaldehyde from acetylene and water by the use of mercury salts as catalysts the chief drawback is the ease with which the mercury salt is reduced to metallic mercury with consequent loss in activity. It is now shown that mercuric sulphate in sulphuric acid is the most suitable catalyst on account of its activity and less ready reduction but the difficulty attached to its use is the impossibility of separating acetaldehyde from the more concentrated acid solu- tion and the rapid reduction of the mercury compounds in dilute acid solutions. In such solutions the mercury is soon converted into an organic compound and this compound acts as the catalyst.It is suggested that the reaction may be as follows :OWANIC CHEMISTRY. i. 111 a 2H2S0,. 2C2H2+2H20+O:CH~CH<~fi*so4'Hg>CH*CH:0 4 CHO*CH,*HgCH(CHO)*Hg*CH(CHO)*Hg*CH2*CH0 +H2S04= CHO*CH<E:s 040Hg> CHCHO + 2CH,*CH 0. It is considered that the reduction of mercury compounds by acetylene is in some way due to their hydrolysis in dilute acid solutions and the only way in which acetaldehyde could be obtained without the reduction of any mercury salt whatever was by the action of a stream of moist acetylene a t 70-120" on a dry mixture of the mercuric sulphate-acetylene compound and sodium potass- ium or ammonium hydrogen sulphates. This process was how- ever so slow as not to be of practical value. Owing to the difficulty of obtaining the acetaldehyde from these acid solutions it was found advantageous to use the solutions in place of pure acetaldehyde in the preparation of quinaldine.For this purpose aniline sulphate was dissolved along with the mercuric sulphate in sulphuric acid before passing in the acetylene a con- centration of 40% of sulphuric acid and a temperature of 60' being most advantageous. For the preparation of paracetaldehyde a large bottle or carboy was filled with dry fragments of glass on which a pasty mass of mercuric sulphate sodium or ammonium hydrogen sulphate and a very little water was distributed and the moist acetylene led in with shaking. The paracetaldehyde accumulated as a separate layer a t the bottom of the bottle. The aldehyde-mercury ratio obtained was 17 1 with a steady production of paracetaldehyde. I n this method no distillation process is necessary there are no by-products or waste products and there is no excess of acetylene to be recovered. W.G. Preparation of Aldol from Acetaldehyde. NATHAN GRUNSTEIN (Brit. Pat. 147 119) .-&do1 condensation by means of a very small quantity of an alkaline catalyst proceeds without the addition of ice or a neutral organic diluent as a smooth and easily controlled reaction if the acetic acid contained in the acetaldehyde is f i s t neutralised with the requisite quantity of sodium hydroxide solution and the catalyst is then gradually added with cooling the operation being preferably conducted in an atmosphere of nitrogen to prevent the formation of further quantities of acetic acid by atmospheric oxidation.As catalyst aqueous alkali hydr- oxide not exceeding in quantity 1 part of alkali to 100 parts of acetaldehyde may be employed or equally favourable results are obtained with alkali or alkaline-earth carbides or cyanides or alkaline-earth hydroxides. In all cases the presence of a small e* 2i. 112 ABSTRACTS OF CHEMICAL PAPERS. quantity of water appears to be essential. To prevent the con- densation proceeding too far with formation of resins etc. it is stopped before all the acetaldehyde has been converted into aldol bv adding sufficient hvdrochloric or acetic acid to neutralise the akali sepvarating the salt and distilling the product' in a vacuum. G. F. M. Preparation of Butaldehyde and Butyl Alcohol from Crotonaldehyde. NATHAN GRUNSTEIN (Brit.Pat. 1471 18) .- Butaldehyde and butyl alcohol are obtained in good yield by the catalytic hydrogenation of crotonaldehyde in presence of 20-25% of water or steam. The formation of undesirable by-products of high boiling point is greatly rninimised by using a large excess of hydrogen and the excess passing from the catalyst can be recircu- lated after suitable cooling to condense the reaction products. The catalyst is prepared by depositing in the usual manner 5-15 parts of nickel on 100 parts of pumice or kieselguhr and the optimum temperature for the hydrogenation is 110-120". Instead of using a mixture of pure crotonaldehyde and water the product of the decomposition of aldol may be employed with equal advantage. The reaction may be carried out either in a tube charged with the contact material or with the liquid substances in an autoclave the hydrogen in the latter case being pumped in a t 10-15 atm.pressure with vigorous agitation of the liquid. In either case provision must be made for the periodical discharge of gas from the apparatus as the hydrogen becomes contaminated with propyl- ene and carbon monoxide produced bv the "cracking:" of the v crotonaldehyde particularly i t the high& temperatures. G. F. M. Benzyl Ethers of Carbohydrates. M. GOMBERG and C. C. BUCHLER ( J . Amer. Chem. Soc. 1921 43 1904-1911-).-Carbo- hydrates of all types are readily benzylated and various benzyl ethers obtained when the carbohydrate is heated with benzyl chloride and aqueous sodium hydroxide for several hours a t about 90".Thus a-methylglucoside yielded benzylglucoside dibenxyl- rnethylglucoside and tetrabenxyl- benxylglucoside. Sucrose gave a solid dibenxyl and a liquid pentubenxyl derivative. Dextrin gave a benxyldextrin C1,Hl9O1.,-,*C,H m. p. 208-210" ; potato starch gave a monobenxyl derivative C,,H,,O~,*C,H m. p. 200-203" and maize starch gave a dibenxyl derivative C12H18010(C,H7)2 m. p. 203-205". Cellulose unless previously subjected to one of the several so-called " hydration " processes underwent only slight benzylation but after hydration a monobenzgl a tribenxyl and a tetrabenzyl derivative were obtained according to the conditions. Benzylated cellulose unlike cellulose itself is insoluble in Schweizer's reagent. W. G. Biochemical Synthesis of a-Methyl-d-mannoside.H. H~RISSEY ( C m p t . rend. 1921 173 1406-1407; cf. A. 1921 i 306) .-By the action of a-methyl-d-mannosidase present in theORGANIC CHEMISTRY. 1. 113 germinated seeds of lucerne on a solution of mannose in 10% methyl alcohol the author has synthesised a-methyl-d-mannoside and obtained it in a crystalline form. The Formation of Osazones. MARC H. VAN LAER and R. LOMBAERS (Bull. Xoc. chim. Belg. 1921 30 296-301).-A study of the formation of the osazones of levulose and dextrose shows that the difference in the time of the reaction has its origin a t the second stage and is due to the fact that the oxidation by the second molecule of phenylhydrazine is in the first case that of a primary alcohol and in the second that of a secondary one. Pentosans. EmL HEUSER ( J .pr. Chern. 1921 [ii] 103 69-102) .-[With NARIA B ~ ~ ~ ~ ~ . ] - s a l k o w s k i ' s method for the preparation of xylan from wheat straw (A. 1902 i 206) yields a product which gives a t most 80% of the theoretical proportion of furfuraldehyde and contains appreciable amounts of ash. The author finds that application of a modification of Sallcowski's method to bleached straw cellulose [Xtrohxellstqfl] (cf. Heuser and Haug 2. angew. Chem. 1918,31,99) is capable of yielding a product containing 96% of xylan calculated on the dry ash-free material and 0.35y0 of ash. [With E. KURSCHNER.]-BY 43 yo hydrochloric acid solution (d 1-21> a t the ordinary temperature xylan cannot be hydrolysed completely to xylose since part of the latter is destroyed before the hydrolysis is finished.The results obtained when the course of the hydrolysis is followed by measuring the copper-reducing power and by estimation of the furfuraldehyde obtained by treat- ment with hydrochloric acid show that no sugar other than xylose is formed during the hydrolysis but fail to indicate the nature of the 4% of non-xylan in the preparation. [Cf. J . Xoc. Chem. Ind. 1922 Feb.] T. H. P. Chemistry of Starch. IV. The Methylation of Poly- amyloses. HAXS PRINGSHEIM and WALTER PERSCH (Ber. 1921 54 [B] 3162-3168; cf. A. 1912 i 832; 1913 i 1156; 1915 i 382) .-Tetra-amylose is not converted into a homogeneous product by sodium hydroxide and methyl sulphate. If however the material which is thus obtained containing 28% OMe is treated with methyl iodide and silver oxide it gives a crystalline substance which contains two methoxyl groups in each dextrose residue.Very protracted treatment does not bring about methylation of the third hydroxyl group. The most impvrtant observation how- ever is that the treatment does not cause depolymerisation and that in accordance with determinations of the molecular weight in freezing benzene or naphthalene the product is to be regarded as octumethyltetra-amylose. It crystallises in colourless hexagonal plates which do not decompose below 250" and has [a]2,0+141*5 to +148.2" in ethyl alcoholic solution. The slight mutarotation is somewhat surprising since the original tetra-amylose is not mutarotatory. Fermentation of starch by a degenerated specimen of Bacillus W. G. H. J.E.i. 114 ABSTRACTS OF CHEMICAL PAPERS. mucerans has led to the isolation of a tetra-amylose which gives a dark green crystalline additive compound with iodine and after being freed from the latter a crystalline additive product with carbon disulphide. Removal of the latter gives a tetra-amylose crystallising in needles and having a specific rotation higher by a few degrees than that quoted for previous specimens. The sub- stance is possibly a stereoisomeride but its preparation is difficult and uncertain. H. W. Preparation and Alkyl Interchange of Cellulose Esters; Cellulose Stearate and Laurate. AD. GRUN and FRANZ WITTKA (2. angew. Chem. 1921 34 645-648; cf. A. 1921 i 222).-The attempt to find a simple method for the preparation of cellulose esters of the higher fatty acids has led to observations on the interchange of alkyl groups between cellulose esters and alcohols and between alkyl esters and cellulose.Cellulose esters of the higher fatty acids are formed by acylation of cellulose with an acid chloride and pyridine. Preliminary experiments with stearyl chloride led to impure monostearate and mixtures of cellulose mono- and di-stearate; the pure distearate was only obtained by the use of a large excess of the acid chloride the reaction mixture being diluted with benzene. Cellulose di- stearate forms white fibres m. p. 220" (decomp.) is insoluble in the usual cellulose solvents even in an ammoniacal solution of copper oxide but soluble in fatty acids and in glycerides on heat,ing a t about 200". The fibres under the microscope are cylindrical and swollen to two or three times the original volume and the lumen has partly disappeared.Cellulose dilaurate is a white spongy short-fibred mass m. p. about 250". The solubility in glycerides is greater than that of the distearate and when dis- solved in triisovalerin and diluted with alcohol a faintly coloured powder is obtained m. p. 110". Cellulose distearate and dilaurate exhibit a characteristic behaviour with fat colouring matters for with Sudan-I11 an intense scarlet-red coloration is produced which is not removed by treatment with 50% alcohol whereas cellulose or cellulose steeped in fatty acids is only faintly coloured and the colour is completely removed by 50% alcohol. These cellulose esters may be distinguished further from cellulose by their behaviour with iodine and sulphuric acid for they are coloured wine-red and the fibre swells but little and is not disintegrated by the acid.The interchange of alkyl groups between ethyl esters of fatty acids and cellulose does not proceed as readily as with glycerol. Alkyl interchange between the cellulose esters of the lower fatty acids and alcohols proceeds readily however but the esters of the higher fatty acids react with difficulty. Thus cellulose triacetate and ethyl alcohol yield cellulose monoacetate whereas under similar conditions but little stearic acid is removed from cellulose distearate. The stability of the cellulose esters increases with their molecular weight. When isoamyl alcohol reacts with cellulose triacetate alkyl interchange occurs but is accompanied by a far-reaching degradation of the cellulose molecule.F. M. R.ORGANIC CHEMISTRY. i. 115 Plant Colloids. XII. Action of Formaldehyde on Cellu- lose. M. SAMEC and S. FERJAN~I~ (Koll. Chem. Beihefte 1921 14 209-226; cf. A. 1921 i 400 707).-Purified sulphite cellulose has been heated under pressure with formaldehyde or formic acid a t 143" for various periods of time and the products have been compared with the original cellulose. It is shown that formaldehyde reacts with cellulose and its derivatives when they have been converted into the emulsoid condition. The product does not give any iodine coloration but after washing away the formaldehyde the colour can be obtained after the product has been emulsified by sulphuric acid.The sulpholysis of cellulose in the presence of formaldehyde takes place differently from the action in its absence and leads to low molecular derivatives. The charring of cellulose derivatives by strong sulphuric acid is strongly retarded by formaldehyde and in the same way the esterification of cellulose derivatives is also retarded. Formaldehyde has a similar action on cellulose derivatives. The experimental results are explained by the assumption that the formaldehyde unites to the cellulose with the breaking of oxygen rings and the formation of oxymethylene groups and that in the cellulose molecule an internal anhydride formation follows with the hydroxyl group of a neighbouring dextrose residue. Alkaline Copper Hydroxide Solutions and Copper Oxide- Ammine-Cellulose Solutions.WILHELM TRAUBE (Bey. 1921 54 [B] 3220-3232).-The term " alkaline copper hydroxide solutions " is applied to the aqueous solutions produced from polyhydroxy-compounds copper oxide or hydroxide and alkali hydroxides. The quantity of copper hydroxide dissolved by solutions of glycerol and potassium hydroxide in which the con- centration of the latter is maintained constant increases with increasing molecular ratio of alkali to glycerol within certain limits; it diminishes with increasing dilution of the alkali. Since copper hydroxide is not soluble in glycerol or in alkali hydroxide solutions of the concentration used it appears that the action depends on the initial formation of alkali glyceroxide and reaction of the latter with copper hydroxide to give an alkali-copper glyceroxide.The behaviour of polyhydroxy-alcohols and of polyhydroxy-compounds in general is similar to that of glycerol. The place of the fixed alkalis can be taken by the ethylenediamine hydroxide of copper (A. 1912 i 9) since it is found that addition of glycerol enables a solution of ethylenediamine saturated with copper hydroxide to dissolve considerably further amounts of the substance. A similar effect is produced. by mannitol or sucrose. The solubility of cellulose in a solution of the ethylene- diamine hydroxide of copper is also to be attributed to the for- mation of an alkoxide compound of the polyhydroxy-compounds produced by the degradation of cellulose since it is found that a solution of ethylenediamine saturated with copper hydroxide has the power of dissolving more of the latter after being treated with cellulose.The ability to dissolve cellulose is however a specific J. F. S.i. 116 ABSTRACTS OF CHEMICAL PAPERS. property of the copper solutions since the ammine compounds of other metallic hydroxides which in all probability are able to give rise to akoxide derivatives do not possess this power. The same conception of the solution of cellulose must be extended also to Schweizer’s solution. Since copper hydroxide is relatively but little soluble in aqueous ammonia i t is not possible to obtain concentrated solutions of cellulose directly. Such solutions can however be obtained by taking advantage of the fact that Schweizer’s solution saturated with cellulose has the power of dissolving further amounts of both cellulose and copper hydroxide.The explanation of the phenomenon is found in the existence in solution of an equilibrium Cu( OH),+4NH3 e [Cu(NH,),](OH) ; in proportion as the ammine is removed in combination with cellulose or the products of its degradation the equilibrium is displaced towards the right-hand side of the equation and further quantities of copper hydroxide can be dissolved. The insolubility of cellulose in copper ammine solutions which have been treated with glycerol is due to the fact that the copper is now present as the glyceroxide. The precipitation of cellulose from its solution in Schweizer’s reagent by glycerol is likewise explained. Soluble starch behaves towards alkaline copper hydroxide solution in the same manner as the other polyhydroxy-compounds.Ordinary starch swells and becomes intensely blue when brought into contact with ethylenediamine solution saturated with copper hydroxide; the colour is not removed by repeated washing with water. The substance contains nitrogen and possibly is a well- defined compound of alkoxide nature. Cellulose. VI. De-polymerisation of Ethyl-cellulose. KURT HESS and WALTER WITTELSBACH (Ber. 1921 54 [B] 3232-3241).-In a previous communication (A. 1921 i 710) the depolymerisation of ethyl-cellulose has been described and substances with a molecular weight in dilute solution of 800- 900 have been isolated. Since however the molecular weight increased rapidly with increasing concentration owing. to associa- tion it remained doubtful whether still lower values would be observed in more dilute solution and the uncertainty was increased by the subsequent discovery (this vol.i 12) of the ready con- version of cellulose by acetyl chloride into a compound of the composition and molecular weight of a biose-anhydride. It is now shown that the products of acetolysis of ethyl-cellulose after action varying in its duration from two to one hundred and forty- four hours have molecular weights in very dilute solution corre- sponding with those required for a tetraethylbiose anhydride. De-polymerisation of cellulose to “ celluxose ” occurs therefore with much greater readiness than has been assumed previously. H. W. H. W. Mercury Fulminate. HANS RATISBURG (Ber. 1921 54 [B] 3185-3187).-The presence of unsaturated impurities in mercury fulminate can be detected by the behaviour of thei.117 ORGANIC CHEMISTRY. specimen towards potassium permanganate which is not affected by the pure compound. The amount of oxidising agent used by impure specimens depends on the medium in which they are suspended and generally is greatest in acid and least in aqueous suspension. On the other hand the addition of halogen cannot be applied quantitatively since pure mercury fulminate unites with halogen. Nevertheless tit'ration with iodine is a useful method of detecting the presence of more reactive mercury salts which is judged by the presence of greater or less quantities of red mercuric iodide in the titrated mixture. The following process is more convenient than that advocated by Solonina for the estima- tion of oxalate in mercury fulminate.The specimen (about 3 grams) is dissolved in ammonia (20%) and the bulk of the fulminate in so far as it is not decomposed is re-precipitated with acetic acid. Oxalic acid is precipitated in the clear filtrate (or an aliquot portion thereof) with approximately N-calcium chloride and the calcium oxalate is weighed as such or as calcium oxide. H. W. Preparation of Guanidine Nitrate. TENNEY L. DAVIS ( J . Amer. Chem. Soc. 1921 43 2234-2238) .-Guanidine nitrate may be obtained in excellent yield by heating dicyanodiamide with slightly more than two molecular proportions of ammonium nitrate for two hours a t 160" using either the dry materials alone or with water in an autoclave. At lower temperatures diguanide nitrate is the main product.The reaction consists in the formation of diguanide nitrate by the action of one molecule of ammonium nitrate and this then reacts with the second molecule of ammonium nitrate at the higher temperature to give guanidine nitrate. The reaction is not therefore dependent on the depolymerisation of dicyanodiamide as suggested by Werner and Bell (T. 1920,118 1133) in their account of a similar preparation of guanidine thiocyanate. W. G. The Synthesis of a Nitrogenous Principle of Plants Wydrocyanic Acid by the Oxidation of Ammonia and Carbo- hydrates Glycerol or Formaldehyde. R. FOSSE (Compt. rend. 1921 173 1370-1372; cf. A. 1919 i 152 313 459; 1920 i 664 ii 714 779; 1921 i 165 321 500 652).-In the presence of a silver or a mercury salt ammoniacal solutions of dextrose sucrose starch dextrin glycerol or formaldehyde on oxidation by potassium or calcium permanganate give cyanides as one of the products. W.G. Synthesis of Hydrocyanic Acid by Oxidation in Ammo- niacal Silver Solution of Alcohols Phenols and &nines. R. FOSSE and A. HIEULLE (Compt. rend. 1922 174 39-41).- It has been shown that by the oxidation of a number of alcohols phenols and amines by potassium or calcium permanganate in ammoniacal solution in the presence of silver nitrate hydrocyanic acid is always formed but in variable amount. The highest yield of hydrocyanic acid was obtained from methylamine. W. G.i. 118 ABSTRACTS OF CHEMICAL PAPERS. The Action of Aqueous Ammonia on Dicyanodiamide. TENNEY L.DAVIS (J. Amer. Chem. Soc. 1921 43 2230-2233),- When dicyanodiamide is heated in a sealed tube a t 150" with aqueous ammonia (d 0.9) it gives first guanylcarbamide and then guanidine carbonate. If the reaction is prolonged the guanidine carbonate reacts with ammonia and carbon dioxide giving in turn ammelide ammeline and finally melamine. W. G. Organic Compounds of Arsenic. VII. Additive Com- pounds of Iodoform and Salts of Organic Bases of Tervalent Elements. WILHELM STEINKOPF and GUSTAV SCHWEN (Ber. 1921 54 [B] 2969-2975; cf. this vol. i 71 72).-Attempts to convert tetramethylarsonium tri-iodide into the corresponding monoiodide by means of alcoholic potassium hydroxide solution have led to the isola- tion of an additive compound of molecular proportions of the latter and iodoform.Similar products can be obtained from quaternary ammonium phosphonium and stibinium iodides and in certain cases from the corresponding bromides. These compounds may also be produced from their components or from a mixture of the tertiary arsine methyl iodide and iodoform. They are pale yellow to yellow crystalline substances which can be recrystallised without decomposition from organic solvents but are decomposed by water with separation of iodoform. They are for the most part odourless. Their physiological action appears to be attribut- able to iodoform poisoning. The following individual compounds are described. Tetra- methylarsonium iodide iodoform I[Me,As] ... .CHI m. p. 165" (discoloration). Phenyltrimethylarsonium iodide iodoform yellow needles m.p. 143-145" prepared by the methods indicated above or from phenyltrimethylarsonium hydroxide and iodof orm in alcoholic solution. Triphenylmethylarsonium bromide colourless crystals m. p. 195". Triphenylmethylarsonium bromide iodoform pale brownish-yellow leaflets m. p. 124". Tetramethylammonium iodide iodoform yellow needles m. p. 237" after previous darkening when rapidly heated. Tetraethylphosphonium iodide iodoform m. p. 212-215" after previous darkening when rapidly heated. [Tetraethylphosphonium bromide crystallises in colourless needles m. p. about 320' (decomp.).] Tetraethylphosphonium bromide iodoform brownish-yellow powder m. p. about 200" after incipient decomposition at about 180". Tetraethylstibinium iodide iodoform yellow powder m.p. (indefinite) 162" after previous softening. It was not found possible to isolate additive compounds from iodoform and phenyltrimethylarsonium bromide or chloride tetraethylammonium chloride or triphenylmethylarsonium chloride respectively. H. W. Some Recent Applications of Magnesium in Synthetic Organic Chemistry. HARRY HEPWORTH ( J . SOC. Chem. Ind. 1922 41 7-11).-A r6sumG of some of the receot applications of the Grignard reagents.ORGANIC CHEMISTRY. i. 119 Organo-derivatives of Thallium. 111. Some Thallium- dialkyl Salts and the Preparation of Thalliumdiaryl Haloids. ARCHIBALD EDWIN GODDARD (T. 1922,121 3640). Mixed Brganometallic Compounds of Aluminium. FAILLEBIN (Compt. rend. 1922 174 112-114).-Aluminium dissolves in an anhydrous mixture of ether and methylene iodide the reaction being but there is a secondary action in which ethylene is formed If the methylene iodide is replaced by methylene bromide the action is more difficult to start and the secondary action is less marked.These complex compounds are obtained as dense liquids which are readily decomposed by water giving methane. A similar decomposition occurs with alcohol. The compounds are unsaturated and form additive compounds with iodine which when decomposed by water no longer give methane but methyl iodide CH,:AlBr + I = CH,I*AlBrI CH21*A1BrI+H,0=CH,I+A1BrI~QH. 3CH,Iz+4A1=3CH,:A1 I+A1 I 6CH2I2+4A1= 3CzH,+4A1 I,. W. G. Hydrocarbons of the Semibenzene Group. K. VON AUWERS and K. ZIEGLER (Annalen 1921 425 217-280).-1n continuation of previous work (Auwers and Miiller A.1911 i 621) a number of homologous semibenzene hydrocarbons have been prepared and examined with respect to their physical properties and their capacity for passing into aromatic hydrocarbons by isomeric change. The principal physical distinction between the semibenzene hydro- carbons and their aromatic isomerides consists in the fact that the former group of compounds have lower densities and therefore (since the refractive indices of the two series are comparable) higher molecular refractions and dispersions than the latter. In general the semibenzene compounds are more volatile than their isomerides. The conversion of semibenzene hydrocarbons into benzene derivatives takes place in the presence of acids with great ease in the case of the simpler members.Higher in the series polymerisa- tion and other side reactions occur simultaneously. In general the isomeric change involves the migration of one methyl group from the gem-dimethyl residue to an adjacent position in the iiucleus; but if both the neighbouring positions are already occupied the mobile group may attach itself to some other nuclear carbon atom Me,/=\-CII,-tMe/-\Me; Me,/=\-CH,-tMe/-\Me A new series of physical constants for carefully purified 1 1- dimethyl-4-methylese-A'~i-cycEohexadie~ie is given b. p. 38- Me Me Me Me \=/- \-/ \=/- \-/ - Me Mei. 120 ABSTRACTS OF CHEMICAL PAPERS. 40"/15 mm. dt5'8 0.8360 di0 0.833 1.50295 141739 n15'8 Y This hydrocarbon passes into +-cumene with development of heat when a drop of hydrochloric acid is added to its solution in two vols.of acetic acid. 1 l-Dimethyl-4-ethyZ-A2~5-cyclohexadien-4-ol large transparent tablets m. p. 4 6 4 7 ' is prepared like the trimethyl compound (loc. cit.); on shaking with 10% sulphuric acid it is converted into 1 1 -dimethyl-4-ethylidene-A2:5-cyclohexadiene b. p. 71- 74"/16 mm. 81-5-84"/25 mm. di5.I5 0-8614 d;O 0.867 n;'l5 1-51072 preparation gave slightly different constants e.g. di0 0-855 n$ 1.5124). This hydrocarbon is fairly stable a t 160"; on oxida,- tion by permanganate it is converted into dimethylmalonic acid and acetic acid. When its solution in acetic acid is saturated with hydrogen chloride it is converted in the course of one hour into 1 2-dimethyl-4-ethylbenzene (b. p. 186-187" di5'2 0.8777 dy 0.874 n:'O5 160103 n5'05 1.50489 nf'05 1.51606 ny-O5 1.52531 n$ 1-5027) which was prepared for comparison from 4-0-xylyl methyl ketone by reduction with amalgamated zinc and hydrochloric acid.1 1-DimethyE-4-n-propyl-A2~6-cyclohexadien-4-ol and 1 l-dimethyl-4- n-pr~pylidene-A~:~-cyclohexadiene could not be fully purified (b. p. 95-105"/10 mm. and 83-85" respectively). The crude alcohol was converted into 1 2-dimethyl-4-n-propylbenzene by the addition of a drop of concentrated hydrochloric acid to a solution in acetic acid and the hydrocarbon identified by comparing its physical properties (b. p. 201-203" d:2'85 0.8718 d;O 0.866 n:.? 1.49504 ng.7 1.49881 n;32' 1.50920 n;" 1.51784 niy 1.4955) with those of a specimen pre- pared by reducing 4-o-xylyl ethyl ketone. This ketone b.p. 258- 262' was obtained by the action of propionyl chloride and aluminium chloride on o-xylene and was characterised by means of its semi- carbaxone m. p. 192-193". 1 1 3 4-Tetramethyl-A2~6-cyclohexadien-4-ol needles m. p. 50.5-51.5" was obtained like its lower homologues but could not be converted into the corresponding semibenzene owing to the ease with which this substance passed into its aromatic iso- meride durene. From 1 1 3-trimethyl-4-ethyl-A*~5-cyclohexa- dien-4-01 (m. p. 47-48') however 1 1 3-trimethyl-4-ethyl- A2:5-cyclohexadiene (b. p. 85-86' di2" 0.8844 di0 0-879 n1,2" 1.51470 n:'' 1.51931 n,2' 1.53230 n5.2' 1.54371 n$ 1.5160) was obtained by the usual means. It was converted by hydrochloric acid in the presence of acetic acid into 4-ethyl-+-cumene.The following physical constants are recorded for 1 1 2 4- tetramethyl-A2:5-cyclohexadien-4-ol b. p. 90-95" m. p. below 20" di0'O 0-9333 dp 0.925 n;'l 1.48376 n1,0'l 1.48685 n;" 1.49502 ny'l 1.50176 n$ 1.4824. On treatment with acids it yields 1 1 2- trimethyl-4-methylene-A2 '5-cyclohexadiene (b. p. 60-65" 115 mm. d:'" 0.8735 d?O 0.866 n;O'l 1.51331 1.51813 n:. 1.53213 nSp" 1.54435 ng 1.5139) which readily passes into a polymeride. The isomeric aromatic hydrocarbon isodurene is best obtained therefore from the alcohol. 1.53009 n$ 1.501 1. n15.15 1.51572 n;j5'15 1.53015 ny'15 1.54300 n$ 1.5135 (anotheri. 121 ORGANIC CHEMISTRY. 1 1 3 4 6-Pent~methyl-A~~~-cyclohexadien-4-ol b. p. 85- 95"/12 mm. on dehydration gives 1 1 3 6-tetramethyl-4-methyEent7- A2 6-cyclohexadiene b.p. 77'/12 mm. d:52 0*8809 cZjO 0*877 nz2 1.51235 nZ2 1*51887 nF2 1.53006 ny2 1,54172 qi 1.5147 which isomerises yielding pentamethylbenzene. 1 1 3 &Tetra- methyl-4-ethyl-A2 5-cyclohexadien-4-ol could not be purified by distillation owing to the ease with which it passes into 1 1 3 6- tetramethyl-4-ethylidene-A2 5-cyclohexadiene. This hydrocarbon has the following constants b. p. 100-103"/18 mm. dy' 0.8837 &" 0.880 nz4 1.51028 ng4 1.51452 nF4 1.52702 n;' 1.63796 n" 1.5125. The main product of the action of sodium hydroxide and chloro- form on hemimellithenol is 1 2 6-trimethyl-1-dichlorornethyl-a" '- cyclohexadien-4-one m. p. 107-5-108*5" which gives a semi- carbaxone m. p. 218" and a p-nitrophenylhydraxone m.p. 190- 191". 6-Hydroxy-2 3 4-trimethylbenmldehyde is a by-product in the reaction. It melts a t 77-78' and yields a sernicarbaxone which turns yellow a t 130" but does not melt a t 280'. Magnesium and methyl iodide convert the chloro-ketone into 1 2 4 6-tetra- methyl-1-dichloromethyl- A2 5-cyclohexadien-4-ol which however is partly decomposed during the isolation giving 1 2 3-trimethyl- 5-di-o-chZoroethylbenxene for which the following constants are recorded b. p. 155-159'/19 mm. d f s 1.1424 d$1.144 n 1.53900 n 1.54310 np1.55494 n$ 1.5439. On reducing the above chloro- alcohol two substances are obtained the normal product 1 1 2 4 6-pentamethyl-A2~5-cyclohexadien-4-ol partly undergone dehydration with the formation of 1 1 2 8-tetra- rnethyl-4-methylene-A2 5-cyclohexadiene which when pure has the following constants b.p. 89-90"/15 mm. d:" 0.8765 df 0.879 nzL 1.50884 nc3 1.51350 nF2 1.52660 nvL 1.53830 12 1.5149. When warmed with acetic acid and sulphuric acid this hydrocarbon undergoes isomeric change with the formation of pent amethyl benzene. Constitution of Benzene. RONALD FRASER (T. 1922 121 The Action of Sulphuryl Chloride on Organic Substances. I. Simple Monosubstituted Benzenes. THOMAS HAROLD DURRANS (T. 1922,121 44-49). The Existence and Reactions of Positive Halogen attached to Carbon in Aromatic Compounds. BEN H. NICOLET ( J . Amer. Chem. Xoc. 1921 43 2081-2084).-3-Iodo-p-toluidine 4-iodoaniline aceto - 3 - bromo-p - toluidide and 3 -iodo-4- h y droxy - benzoic acid when boiled with 10% hydrochloric acid are hydro- lysed with a readiness decreasing in the order named in such a way that in part they replace their halogen by hydrogen and in part give di- or tri-halogenated derivatives.This is considered to be the best evidence yet offered for the existence of positive lialogen attached to carbon in the benzene nucleus. It will be having C. K. I. 1 88-1 96).i. 122 ABSTRACTS OF CHEMICAL PAPERS. noticed that in all cases the halogen is in a position ortho or para to a strongly negative group. In similar compounds iodine is more positive than bromine and more positive in ortho- than in para-compounds. Alkali is much less effective than acid in removing such positive halogens. In the presence of stannous chloride and acid the halogen is abnormally readily removed but resubstitution is prevented.W. G. The Action of Pyrosulphuryl Chloride on Toluene. WILHELM STEINKOPF and KURT BUCHHEIM (Ber. 1921 54 2963-2968).- Pyrosulphuryl chloride reacts with toluene a t 60" with evolution of hydrogen chloride and sulphur dioxide. The reaction product is a mixture from which the following substances have been isolated Toluene-p-sulphonic acid toluene-p-sulphonyl chloride a mixture of dichlorotoluenes and 4-chloro-3 4'-ditolylsulphone fine needles m. p. 136" which is also formed by the interaction of o-chlorotoluene and toluene-p-sulphonyl chloride dissolved in light petroleum in presence of aluminium chloride a t 55". A vigorous reaction ensues when toluene is added to a mixture of pyrosulphuryl chloride and aluminium chloride a t -5" to O" with formation of toluene-p-sulphonic acid 0- and p-chlorotoluene pp-ditolylsulphone and a substance needles m.p. 215-217" containing chlorine but no sulphur. F. M. R. Hydrogenated Naphthalenes and their Transformations. I. G. SCHROETER (Annulen 1922 426 l-l'l).-[With G. vOSSEN.]- The condensation between chloral and methyl malonate leads to the formation of methyl 0 3 3-dicyclo-Al-octene-3 7-dione- 2 4 6 8-tetrucarboxylate (I) which can be converted by hydro- lysis and reduction into 0 3 3-dicyclooctane-3 7-dione 0 3 3- dicyclo-octane-3 y-diol and finally 0 3 3-dicyclooctane (11) (b. p. 138" d? 0-8817 nz 1.46632) Closely related to this hydrocarbon (11) are the hydrogenated naphthalenes certain of which moreover are more easily and cheaply prepared.[With F. STAHL H. HAEHN and C. PRIGGE.]-FuU working details are given of the preparation of tetrahydronaphthalene by reducing naphthalene by means of hydrogen a t 180-200" and 5-15 atmospheres in the presence of nickel. The hydrocarbon purified by regeneration from its sulphonic acid has b. p. 100- 101"/25 mm. 206.5" (corr.)/755 mm. cZio 0.971 n 1.5434. C. K. I.ORcfANIC CHEMISTRY. i. 123 Hydrogenated Naphthalenes and their Transformations. 11. Nitro- and Amino-derivatives of Tetrahydronaphthalene. G. SCHROETER [with E. KINDERMANN C. DIETRICH C. BEYSCHLAG CL. FLEISCHHAUER E. RIEBENSAHM and c. OESTERLIN] (Annalen 1922 426 17-83).-This paper describes the nitration of tetra- hydronaphthalene the reduction of various mono- di- and tri- nitro-derivatives and the nitration of the acetyl derivatives of the amines so obtained. The orientations of a considerable number of isomeric nitro-compounds amines and nitroamines are definitely established.The mononitration of tetrahydronaphthalene using a mixture of nitric and sulphuric acids leads to the formation of both 1- and 2-nitro-ar-tetrahydronuphthalene which may be separated by frac- tional distillation and " freezing out " the fractions or by taking advantage of the fact that the 2-nitro-compound is more easily reduced than its isomeride to an amino-derivative. 1 -Nitro-ar- tetrahydronaphthalene has m. p. 34" b. p. 157"/13 mm. d 1.1757 and the 2-compound m. p. 31-4" b. p. 169"/13 mm. d$ 1.1762. On dinitration tetrahydronaphthalene yields a mixture of 1 2- dinitro-ar-tetrahydronaphthalene (m.p. 102-103") and 1 3-dinitro- ar-tetrahydronaphthalene (m. p. 95') which may be separated by crystallisation from concentrated sulphuric acid in which the former is less soluble. The orientation of the 1 2-compound rests on its reduction to ar-tetrahydro- 1 2-naphthylenediamine and 1-nitro-ar-tetrahydro-P-naphthylamine (see below) and that of the 1 3-isomeride on its oxidation to 3 5-dinitrophthalic acid and its reduction to the 1 3-diamine and the l-nitro-3-amino- compound (see below). Another oxidative fission which the 1 3-dinitro-compound undergoes with nitric acid leads to the form- ation of P-o-carboxytrinitrophenyZpropionic acid which decomposes violently on heating and is characterised by analysis of its potassium hydrogen salt.1 3-Dinitro-ar-tetrahydronaphthalene cannot be further nitrated but the 1 2-isomeride may be converted into 1 2 4-trinitro-ar-tetrahydronaphthdene m. p. 94-5-95" the struc- ture of which is established by its conversion into the triamino- derivative (see below). The other possible isomeride namely 1 2 3-trinitro-ar-tetrahydronaphthalene is not produced by direct nitration. 1 1-Hydraxo-ar-tetrahydronaphthalene which is obtained by reducing 1. -nitro-ar-tetrahydronaphthalene by means of zinc dust and alkali forms colourless slender needles m. p. 181-1-83" and on oxidation by permanganate is converted quantitatively into 1 1-am-ar-tetrahydronaphthalene. The latter which crystallises in glistening red needles m. p. 190-191' may also be obtained along with 1 1 -azoxy-ar-tetrahydronaphthaZene yellow needles m.p. 184' by reduction of the nitro-compound with zinc and alkali hydroxide under less energetic conditions. The benzidine conver- sion applied to hydrazotetrahydronaphthalene gives rise to 4 4'- diamino-1 1'-di-ar-tetrahydromphthyl m. p. 153-154" the hydro- chloride hydrobromide sulphate and phosphate of which are described. The corresponding diazonium salt gives substantive dyes on couplingi. 124 ABSTRACTS OF CHEMICAL PAPERS. with naphthionic acid Neville and Winthers's a-naphtholsulphonic acid crocein acid H-acid salicylic acid chromotropic acid " P-aminonaphtholsulphonic acid " and G-acid 4 4'-dihydraxino- 1 1 '-di-ar-tetrahydronaphthyl on reduction by means of stannous chloride and 4 4'-diethoxy-l 1'-di-ar-tetrahydronaphthyl colourless needles m.p. 173" on decomposing with ethyl alcohol. A basic by-product consisting of colourless needles m. p. 216" and giving a hydrochloride which is easily soluble in water is obtained in the preparation of 4 4'-diamino-1 1'-di-ar-tetrahydronaphthyl. Apparently it is 1 l'-diamino-2 2'-di-ar-tetrahydromphthyl because when heated its hydrochloride yields ammonium chloride and a carbazole-like base which may be separated in the form of its picrate. ar-Tetrahydro-a-naphthylamine and ar-tetrahydro-p-naphthyl- amine are obtained from the corresponding nitro-compounds by catalytic reduction and may also be obtained by reducing the crude mononitration product of tetrahydronaphthalene and separ- ating the isomeric bases by taking advantage of the differences of solubility of their hydrochlorides in water their methanedisul- phonates in 96% alcohol and the difference in the ease with which the bases are acetylated.ar-Tetrahydro-a-naphthylamine b. p. 146"/12 mm. gives a hydrochloride which is more easily soluble than that of the P-derivative and a methanedisulphonate which forms colourless leaflets soluble in 20 parts of hot water 60 parts of cold water and about six times as soluble in alcohol as the @-compound. With phthalic anhydride the base gives a phthalamic acid CloHll*NH~CO*C,H,*CO,H colourless needles m. p. 182- 184" (decomp.) which on heating passes into the phthalimide (needles m. p. 148-150") by loss of water. ar-Tetrahydro-a- naphthylamine is more easily acetylated than the P-compound and its acetyl derivative (m.p. 156") on methylation by the action of methyl sulphate on its sodio-derivative gives the acetyl derivative of ar-tetrahydro-a-mphthylmethylamine which has m. p. 70-72" and b. p. 182-185"/11 mm. The hydrochloride and sulphate of ar-tetrahydro-p-naphthylamine (b. p. 147-148"/13 mm. m. p. 38.5-39.5") are sparingly soluble in cold water and the methane- dithionate is rather sparingly soluble in alcohol. The phthalamic acid forms glistening needles m. p. 156*5-158-5" and the phthulimide needles m. p. 169-171". The acetyl derivative (m. p. 102-104") on methylation yields the acetyl derivative of ar-tetrahydro- P- naphthylmethylaamine needles m. p. 67-69". The preparation of aceto -4-nitro-ar- tetrahydro - u-naphthalide by nitration of aceto-ar-tetrahydro-a-naphthalide has been described by Green and Rowe (T.1918 113 %S) but it is now shown that nceto-2-nitro-ar-tetrah ydro- a-mphthalide (colourless needles m. p. 18P-185") and aceto-3-nitro-ar-tetrahydro-a-naphthlide (colourless needles m. p. 193") are formed as by-products. 2-Nitro-ar-tetra- hydro-a-naphthylamine which is. obtained by hydrolysis of its acetyl derivative forms orange needles m. p. 87-88'. Its con- stitution rests on its relationship to ar-tetrahydro- 1 2-naphthylene- diamine (see later). 3- Nitro-ar-tetrahydro- u-naphthylamine preparedORGANIC CHEMISTRY. i. 125 by hydrolysis of its acetyl compound forms yellow leaflets m. p. 78". It is identical with the product obtained by regulated reduc- tion of 1 3 - dini tro - ar- t e trah ydronap ht halene .The course pursued by the nitration of aceto-ar-tetrahydro-p- naphthalide varies with the conditions. If glacial acetic acid is the solvent aceto-3-nitro-ar-tetrahydro-P-naphthalide long yellow needles m. p. 134-135*5" is the main product whilst aceto-l- nitro-ar-tetrahydro-p-naphthalide colourless needles m. p. 128-129" is produced only in small amount. On the other hand if the nitration is carried out in the presence of concentrated sulphuric acid the main product is aceto-4-nitro-ar-tetrahydro- p-naphthalide which forms long colourless needles m. p. 194" whilst the 3-nitro- compound is a by-product. 3-Nitro-ar-tetrahydro-p-naphthylarnine the constitution of which follows from its reduction to the diamine (see below) forms long red needles m.p. 125-127'. 1-Nitro- ar-tetrahydro-p-naphthylamine red needles m. p. 96" is obtained not only by hydrolysis of its acetyl derivative but also by partial reduction of 1 2-dinitro-ar-tetrahydronaphthalene. The structure assigned is based on its reduction to the diamine which is known. 4- Nitro-ar-tetrahydro- p-nuphthylamine m. p. 55" obtained by hydrolysis of its acetyl compound is identical with the substance produced by partial reduction of 1 3-dinitro-ar-tetra,- hydronaphthalene. 1-Nitro-ar-tetrahydronaphthalene is obtained when the amino-group is eliminated by diazotisation and subsequent reduction. Aceto- 1 3-dinitro-ar-t.$rahydro- p-naphthalide colourless needles m. p. 189-191" is produced by further nitration of aceto-l-nitro- ar-tetrahydro-p-naphthalide and aceto-3-nitro-ar-tetrahydro-p- naphthalide and as a by-product in the dinitration of aceto-ar- tetrahydro-p-naphthalide.When it is prepared from the 3-nitro- compound an isomeride C,,HI,O,N of unknown constitution and having no definite melting point (decomp. at about 215") is also formed. 1 3-Dinitro-ar-tetrahydro-p-na~hthylamine~ which forms yellow needles m. p. 166-168" is obtained by hydrolysing the acetyl compound. On reduction it yields 1 2 3-triamino-ar- tetrahydronaphthalene (below). Aceto-3 4-dinitro-ar-tetrahydro-p-mphthalide needles m. p. 175- 177" is the main dinitration product of aceto-ar-tetrahydro-p- naphthalide and is also obtained by nitration of aceto-4-nitro- ar-tetrahydro-p-naphthalide. On hydrolysis it yields 3 4-di- nitro-ar-tetrahydro-p-mphthylamine which melts at 157" and on reduction is converted into.1 2 S-triamino-ar-tetrahydro- naphthalene. ar-Tetrahydro-2 3-nuphthylenediamine (for formation see above) has m. p. 135-136" and b. p. 165"/13 mm. Its hydrochloride crystallises in glistening leaflets. With acetic acid it forms 2- methyl - p (3- ar-tetrahydromphthiminaxole (m . p. 25 1-252 ") and with p henanthraquinone 2 3 - ar-tetrahydronaphthylenphenanthraxine CloH8<N:~.~6H* NDC H (m. p. 214-216'). Acetyl-ar-tetrahydro-1 2- nuphthylenediamine m. p. 149-151 O on acetylation yields the 6 4i. 126 ABSTRACTS OF CHEMICAL PAPERS. diacetyl derivative and on hydrolysis gives the free diamine which forms a phenunthraxine m. p.222.9-230". ar-Tetrahydro- 1 3-nuphthylenediamine prepared by reduction of the dinitro-compound forms pearly leaflets m. p. 84-85" b. p. 199-202"/10 mm. Its 1-acetyl derivative obtained from 3-mtro- aceto-ar-tetrahydro-a-naphthalide has m. p. 173" and its 3-acetyl derivative prepared from aceto-4-nitro-ar-tetrahydro- p-naphthalide has m. p. 110-111". The diacetyl derivative obtained by acetyla- tion of any of the above three substances forms small fila- mental needles m. p. 245-246". The monoacetyl derivative of ar-tetrahydro- 1 4-naphthylenediamine is prepared by reducing aceto-4-nitro-ar-tetrahydro-a-naphthalide and has m. p. 154- 156". 1 2 3-Triamino-ar-tetrahydronuphthalene which is produced by reduction of 3 4-dinitro- or 1 3-dinitro-ar-tetrahydro-p-naphthyl- amine is unstable in air but yields a crystalline hydrochloride and a triacetyl derivative which forms microscopic white needles m.p. 285". 1 2 4-Triamino-ar-tetrahydronuphthdene is obtained by reducing the 1 2 4-trinitro-compound or the 2 4- dinitro- 1-amino-derivative (see above). This base is also unstable. but its triacetyl derivative forms small needles m,p. 315". C. K. I. Hydrogenated Naphthalenes and their Transformations. 111. Tetrahydronaphthalenesulphonic Acids Tetrahydro- naphthols and their Derivatives. G. ~CHROETER [with SVANOE H. EINBECK H. GELLER and E. RIEBENSAHM] (Annalen 1922,426 83-160).-Both ar-tetrahydronaphthalene-1 -sulphonic acid which has been prepared already by an indirect process by Morgan Micklethmait and Winfield (T. 1904 85 736) and ar-tetrahydro- naphthalene-2-sulphonic acid (hitherto unknown) are obtained as their chlorides when chlorosulphonic acid is allowed to react with tetrahydronaphthalene. On the other hand concentrated sulphuric acid gives chiefly the 2-sulphonic acid 4-7% of the 1-sulphonic acid being produced simultaneously.Both sulphonic acids on fusion with alkalis yield the corresponding tetrahydronaphthols and the sulphonyl chlorides on reduction give the tetrahydro- naphthylthiols. The sulphonation of tetrahydronaphthalene therefore opens the way to the preparation of a large number of new aromatic compounds. ar-Tetrahydronaphthulene-2-sulphonic acid separates with 2H,O (m. p. 75") its sodium salt with 1-H,O and its lead salt with fiH,O which is given off a t 130".The barium and ammonium salts crystallise in the anhydrous condition in glistening leaflets. The acid chloride m. p. 58" b. p. 197-200"/18 mm. is obtained when phosphorus pentachloride acts on the acid and on treatment with lOyo ammonia passes into the amide m. p. 135-137". The anilide prepared in similar manner has m. p. 155-156". The mixtures obtained when chlorosulphonic acid isl used for the sulphonation may be separated by crystallisation of the acids from chloroform the 1-sulphonic acid separating first or by pre-ORGANIC CHEMISTRY. i. 127 cipitating the lead salt of ar-tetrahydronaphthalene-l-sulphonic acid by adding aqueous lead acetate to a concentrated solution of the acids or by dissolving the sulphonamides in warm N-sodium hydroxide from which the sodium salt of the 2-sulphonamide separates on cooling.The mixture of acid chlorides may also be reduced by means of zinc and hydrochloric acid to the ar-tetra- hydronaphthylthiols the sodium salts of which on condensation with sodium chloroacetate give the sodium salts of the ar-tetrahydro- naphthylthiolacetic acids. The ammonium salt of the %compound is sparingly soluble and is precipitated if ammonium chloride is added. ar- Tetrahydronap hthyl- 8 -thiolacetic acid forms colourless needles m. p. 75-80"; it may be prepared from pure ar-tetra- hydronaphthalene-2-sulphonyl chloride. ar-Tetrahydronaphthulene- l-thiolacetic acid crystallises as glistening plates m. p. 133-135". ar-Tetrahydronaphthyl-2-thiolacetic acid forms a green solution in fuming sulphuric acid; on diluting boiling and making alkaline with sodium hydroxide the sodium salt of bis-ar-tetrahydrothio- nuphthendisulphonic a,cid is precipitated.When ct-naphthol is reduced by means of two molecules of hydrogen at 200" in the presence of nickel the product consists of about 1 0 yo of ct- keto tetrahydronaphthalene 25-30 yo of ar- tetra - hydro-a-naphthol and a large quantity of tetrahydronaphthalene. At low temperatures the ketone is the main product and it seems probable that it forms an intermediate stage in the production of the hydrocarbon. On reduction by means of sodium and alcohol in moist ether the ketone yields ac-tetrahydro-a-naphthol. ac- Tetrahydro-p-naphthol is the chief product of reduction (by the cat'alytic method) of p-naphthol. ar-Tetrahydronaphthalene-2-sulphonic acid is therefore a valuable starting point in the preparation of ar-tetrahydro- p-naphthol and its derivatives.ar-Tetrahydro- p-naphthol forms a methyl ether b. p. 129-131"/11 mm. prepared'by the use of methyl sulphate an acetate b. p. 158"/14 mm. obtained using acetic anhydride and a crystalline benzoate prisms m. p. 96" b. p. 220-222"/10 mm. which is prepared by digesting the phenol with benzoyl chloride and pyridine. On sulphonation ar-tetrahydro- p-naphthol-3-sulphonic acid is produced. It forms needles (2H,O) m. p. QZ" yields a sparingly soluble sodium salt and a barzum salt (C,,,H,,S,O,Ba) gives strongly coloured axo-dyes with the diazonium salts of p-nitro- aniline sulphanilic acid and naphthionic acid and when heated with hydrochloric acid generates ar - tetrahydro- p -napht hol .2 - Methox y- ar-tetrahydronaphthulene-3-sulphonic acid m. p. 107" is obtained by sulphonating the above-mentioned methyl ether. 1 -Bromo-ar- tetrahydro-p-naphthol m. p. 74" may be prepared either by direct bromination of ar-tetrahydro- p-naphthol in carbon tetrachloride or by desulphonation (using hydrochloric acid) of 1 -bromo-ar- tetra hydro- p -naphthol - 3 -sulphonic acid (sodium salt crys t allises with 3H,O) which is produced by sulphonation of 1 -bromo-ar-tetrahydro-i. 128 ABSTRACTS OF CHEMICAL PAPERS. p-naphthol or alternatively by bromination of ar-tetrahydro- p- naphthol-3-sulphonic acid. On dibromination ar-tetrahydro-p- naphthol yields 1 3-dibromo-ar-tetrahydro- p-naphthol m. p. 37" b.p. 198-201"/15 mm. which may also be prepared by the action of bromine on ar-tetrahydro-~-naphthol-3-sulphonic acid or on 1 -bronio-ar-tetrahydro-~-naphthol-3-sulphonic acid and is char- acterised by a well-crystallising acetate m. p. 87". 1-Bromo-3- nitro-ar-tetrahydro-p-naphthol long yellow needles m. p. 129" is obtained by treating 1-bromo-ar-tetrahydro-p-naphthol-3-sulphonic acid with nitric acid the sulphonic acid group being replaced. The sodium salt forms red leaflets and the methyl etlzer obtained with the aid of methyl sulphate yellow needles m. p. 64". 1-Chloro- 3-nitro-ar-tetrahydro-P-naphtholY which forms yellow needles m. p. 9G" is obtained by chlorinating ar-tetrahydro- p-naphthol-3-sulphonic acid and treating the crude product with nitric acid.On reduction by stannous chloride l-bromo-3-nitro-ar-tetrahydro-(3-naphthol yields a mixture of l-bromo-3-amino-ar-tetrahydro-~-naphtholY which melts at 127" and yields a hydrochloride sulphate and nitrate sparingly soluble in cold water and 3-amino-ar-tetrahydro-p-naphthol which crystallises in leaflets m. p. 202" and gives a hydrochloride and a nitrate easily soluble and a sulphate sparingly soluble in cold water. 1 -Bromo-3-amino-2-methoxy-ar-tetrahydronaphthalene the sulphate of which crystallises with 4H,O is obtained by reduc- tion of the corresponding nitro-compound. 3-Amino-ar-tetra- hydro- p-naphthol may also be prepared by hydrolysing its carbonyl derivative Cl,H,o<~H>CO (bclow) m. p. 196". The piperonyl compound C H < ~ H > C H * C H ~ ~ ~ ~ ~ ~ ~ m.p. 1 60" is obtained from the amino-phenol and piperonal and on methylation with methyl sulphate and alkalis yields 3-piperonylideneamino-2-methoxy- ar-tetrahydronapht halene OMe*CloHI,~N:CH~C,H,:O,CH m. p. 120" which when hydrolysed gives 3-amino-2-methoxy-ar-tetrahydro- naphthalene m. p. 86". l-Arninoar-tetrahydro-(3-naphthol is obtained by coupling ar-tetrahydro-(3-naphthol with sulphanilic acid diazide or with benzenediazonium chloride and reducing the azo-compound. 1 - Benxeneazo-ar -tetrahydro- p -naphthol m . p . 84" gives a monobromo-substitution product m. p. 204" ; l-amino-ar- tetrahydro- p-naphthol forms colourless leaflets m. p. 148" and yields a crystalline hydrochloride and sulphate. An isomeric benxene- axo-ar-tetrahydro-p-naphthol m. p.110" is occasionally also formed ; on reduction it yields l-amino-ar-tetrahydro-p-naphthol m. p. 173") the sulphate of which separates from ZN-sulphuric acid. The carbonyl derivative produced by heating with carbamide forms small red needles rn. p. 188"; it lowers the melting point 189- 190" of the carbonyl derivative of l-amino-ar-tetrahydro-/3-naphthol which is prepared in a similar manner. 1-Amino-2-methoxy-ar- tetrahydronaphthalene is produced by reducing 2-methoxy-a-naph- thylamine (m. p. 54" although 84" is the m. p. recorded in the literature) by means of sodium and amyl alcohol. It has m. p. 64") b. p. 195-200"/20 rum. and on hydrolysis by means of hydro-ORGANIC CHEMISTRY. i. 129 chloric acid a t 180-190" yields 1-amino-ar-tetrahydro- p-naphthol.1 - Nitro-ar- tetrahydronaphthulene- 3-sulphonic acid which may be prepared by directly sulphonating 1 -nitro-ar-tetrahydronaphthalene and is characterised by a crystalline amide m. p. 189" gives ar- tetrahydro-a-naphthylamine-3-sulphonic acid on reduct'ion by means of stannous chloride or by iron and hydrochloric acid but the amino-acid is not converted into 4-amino-ar-tetrahydro-p-naphthol on fusion with alkalis. The main product is ar-tetrahydro-cr- naphthylamine which is also obtained when the amino-sulphonic acid is condensed with p-toluenesulphonyl chloride before fusing with alkalis. However 4-acetylamino-ar-tetrahydro-p-naphthol red needles m. p. 222" is readily produced by the diazo-reaction applied t o 4-acetylamino-ar-tetrahydro- p-naphthylamine (1 -acetyl- derivative of ar-tetrahydro- 1 3-naphthylenediamine preceding abstract) and 011 hydrolysis by means of fuming hydrochloric acid gives 4-amino-ar-tetrahydro-p-naphthol leaflets m.p. 177" which is characterised by having a sparingly soluble hydrochloride. When the unseparated mixture of 1 - and 2-nitro-ar-tetrahydro- naphthalene is sulphonated there is produced along with nitro- sulphonic acid described above an isomeride having a much more soluble sodium salt and consisting in all probability of 2-nitro-ar- tetrahydronaphthalene-4-sulphonic acid. It forms an amide m. p. 21 1-212" and on reduction yields ar-tetrahydro- p-naphthylamine-4- sulphonic acid the hydrochloride of which is soluble in 120 parts of hot water. 1 3-Dinitro-ar-tetrahydro-P-naphthol yellow needles m.p. 141" is produced by adding nitric acid (d 1.4) to a solution of ar-tetrahydro-p-naphthol in sulphuric acid. Its salts are for the most part sparingly soluble in water the sodium potassium ammonium barium and lead salts being easily precipitated. The dry sodium salt on heating with methyl sulphate in toluene yields 1 3-dinitro-2-methoxy-ar-tetrahydronuphthalene which forms colour- less needles m. p. 86.5". On reduction by means of ethereal stannous chloride 1 3-dinitro-ar-tetrahydro-P-naphthol yields 1 -nitro-3-amino-ar-tetrahydro- @-naphthol copper-coloured needles m. p. 127" and in a similar way the nitro-methoxy-compound gives l-nitro-3-amino-2-methoxy-ar-tetrahyd70nhthalene which has m. p. 117" and forms a sparingly soluble hydrochloride. 1 3- Diamino-ar- tetrah ydro- @-nap hthol leaflets m .p . 2 14-2 1 6" is obtained when the dinitro-compound is reduced by alcoholic stannous chloride and 1 3-diamino-2-methoxy- ar-tetrah ydronap h- thalene prisms m. p. 89" when the dinitro-methoxy-derivative is treated similarly or reduced catalytically ; its hydrochloride is obtained as a colourless crystalline precipitate with the aid of ethereal hydrogen chloride. When ar-tetrahydro- p-naphthol is heated under pressure with carbon dioxide in the presence of alkalis 2-hydroxy-ar-tetrahydronaphthalene-3-carboxglic acid m. p. 182" is produced. Its sodium salt crystallises without water of crystallisa- tion and its caZcium salt is sparingly soluble. The methyl ester obtained by direct esterification has m. p. 42" b.p. 179"/15 mm. and forms a sparingly soluble sodium compound ONa*C,oH,o*CO,Me ; the ethyl ester is a liquid b. p. 179"/13 mm. Hydrazine convertsi. 130 ABSTRACTS OF CHEMICAL PAPERS. the methyl ester into a hydraxide OH-C,,H,,*CO*N,H3 m. p. 146" which readily condenses with acetone forming an isopropylidene hydraxone HO*C,,I€,,~CO*NH~N:CMe2 m. p. 235" and on treatment with nitrous acid yields an azide HO*@,,Hlo*CO*N m. p. 99-loo" which on heating eliminates nitrogen and gives the carbonyl derivative of ar-tetrahydro-2 3-naphthylenediamine mentioned above. The hydroxy-acid also yields an anilide m. p. 182-184" an acetyl derivative OAc~Cl,Hlo-C02H m. p. 142-143" and a nitro- derivative 1 -nitro-Z - hydroxy- ar- tetrahydronap hthalene- 3-curb- oxylic acid m.p. 200-202" which on catalytic reduction gives 1-arniizo-2-hydroxy-ar-tetrahydronaphtharboxylic acid. The latter has m. p. 208-ZlO" and is characterised by a sparingly soluble hydrochloride and by a diacetyl derivative NIIAc*C,,HS( CO,H)*OAc m. p. 180-181" which is prepared by acetylating with acetic anhydride in the presence of a trace of sulphuric acid. 4-Amino-ar-tetrahydro-a-naphthol may be obtained by reduction (using stannous chloride) of 4-nitroso-ar-tetrahydro-a-naphthol (m. p. 161-163") which Green and Rowe (T. 1918 113 955) erroneously supposed to be 4-nitro-ar-tetrahydro-a-naphthol or by coupling ar-tetrahydro-a-naphthol with sulphanilic acid diazide and reducing the ar -tetrahydro- p -naphthol -4-axobenxene-p- sulphonic acid so obtained by means of alkaline hyposulphite.The base has m. p. 146.8" and b. p. 208-210"/10 mm. The ethyl ether ( ' ' p - amino-ar - tetrah ydronapht h yl ethyl ether ' ' Jacobsen and Turnbull A. 1898 i 441) may be obtained by ethylating 4-benzene- azo-ar-tetrahydro-a-naphthol with ethyl bromide and alcoholic potassium hydroxide and reducing the product catalytically in the presence of nickel. 2-Amino-ar-tetrahydro-a-naphthol m. p. 110- l l l " is readily obtained by reducing Green and Rowe's 2-nitro- ur-tetrahydro- a-naphthol (loc. cit .) ; its hydrochloride on heating with carbamide yields a carbonyl derivative CloH,,<O->CO NH m. p. 205" which is also produced when ar-tetrahydro-a-naphthol- 2-carboxylazide (see below) is heated in toluene. 3-Acetylamino-ar- tetrahydro-a-naphthol colourless needles m.p. 21 lo is prepared by hydrolysis of the diazonium salt obtained from 3-acetylamino- ar- tetrahydro- a-napht hy lamine (3 -ace t yl derivative of ur - tetra- hydro-1 3-naphthylenediamine preceding abstract). On hydro- lysis with fuming hydrochloric acid it yields S-arnino-ar-tetra- hydro-a-naphthol which forms leaflets m. p. 197" and gives a hydrochloride crystallising in colourless needles. 1-Hydroxy-ar- tetrahydronaphthalene-2-carboxylic acid m. p. 165-166" is obtained by the action of carbon dioxide under pressure on ar-tetra- hydro-a-naphthol in the presence of alkalis. The sodium salt OH*C,,H,,~C02Na,3H20 crystaUises in leaflets. The acetyl deriv- ative OAc*ClOH~,*CO2H obtained with the aid of acetic anhydride has m. p. 170" the methyl ester OH*CloH,o~CO,Me m.p. 56" b. p. 190"/16 mm. ; the hydraxide OH*C,oH,,*CO*N,H3 m. p. 205" ; the isopropylidenehydraxone OH~Cl,H,,*CO*NH*N:CMe2 m. p. 136" ; and the axide OH~Cl,Hl,*CO*N m. p. 84" are prepared like the isomerides previously mentioned. C. K. I.ORGANIC CHEMISTRY. i. 131 Influence of Substitution in the Components on Equilibria in Binary Solutions. XXXIV. The Binary Systems of Anthracene with Nitro-derivatives of Benzene. ROBERT KREMANN and ROBERT MULLER I1 (Monatsh. 1921 42 181-197; cf. following abstract).-In the order of diminishing affinity towards nitro-compounds the hydrocarbons as yet investigated may be arranged in the following order naphthalene acenaphthene phenanthrene and benzene fluorene triphenylmethane and di- phenylmethane. Examination of the binary systems formed by anthracene with nitro-derivatives of benzene and phenol show that anthracene occupies a position in the above series immediately before tri- and di-phenylmethanes.The positions and percentages of anthracene corresponding with the eutectics formed by the binary systems of anthracene with nitrobenzenes are o-dinitrobenzene 1 lo" 12.5% ; m-dinitro- benzene 84" 80/ ; p-dinitrobenzene 146" 35% ; 2 4-dinitro- toluene 66" 9%; 2 4 6-trinitrotoluene 75" 60/,. The system anthracene-1 3 5-trinitrobenzene forms a compound (1 mol. 1 mol.) m. p. l65" which gives a eutectic with trinitrobenzene at 112" containing 4y0 and a eutectic with anthracene a t 162" con- taining 51 yo of anthracene. With 0- (p-)nitrophenol anthracene gives a eutectic at 44" (106") containing 2y0 (6%) of anthracene.With m-nitrophenol a compound (1 mol. 1 mol.) is formed m. p. 187" this giving with anthracene a t 186" a eutectic containing 59% and with m-nitro- phenol a t 93" a eutectic containing 3y0 of anthracene. The system anthracene-2 4-dinitrophenol forms a eutectic a t 101" con- taining 15.5y0 of anthracene. T. H. P. Influence of Substitution in the Components on Equilibria in Binary Solutions. XXXI. The Binary Systems of Triphenylmethane with Amines and Phenols. ROBERT KREMANN FRIEDRICH ODELGA and OTHMAR ZAWODSKY (Monatsh. 1921 42 117-145; cf. Kremann and Wlk A. 1919 ii 458).- The binary systems formed by triphenylmethane with p-toluidine a- and p-naphthylamines and m- and p-phenylenediamines exhibit only simple eutectics.With m-phenylenediamine two liquid layers are formed in the region corresponding with 20-91% of triphenylmethane the temperature of the non-variant equilibrium in this region during the crystallisation of triphenylmethane being 81". Thus of the amines examined only aniline gives a compound with triphenylmethane ; for this system the authors find the maxi- mum temperature 67.5" and for the eutectic between triphenyl- methane and the compound 67" and 72% of triphenylmethane whereas Hartley and Thomas (T. 1906 89 1024) found 71.6" 70" and 71.5% of triphenylmethane respectively. The total affinity between triphenylmethane and aniline is undoubtedly slight and is annulled by the least alteration in the molecular character of the amine. Like diphenylmethane triphenylmethane forms no compounds with phenol a- and p-naphthols the three dihydroxybenzenes,i. 132 ABSTRACTS OF CHEMICAL PAPERS.pyrogallol the three nitrophenols and picric acid. Somewhat extensive miscibility gaps in the liquid condition occur in the binary systems formed by triphenylmethane with resorcinol quinol pyrogallol and picric acid and in some cases solid solutions appear to be formed between triphenylmethane and phenols. The positions of the eutectics in the binary systems formed by triphenylmethane with p-toluidine a- and p-naphthylamines and p - and m-phenylenediamines correspond respectively with the following temperatures and percentages of triphenylmethane 33" 36% ; 37" 33% ; 72" 75% ; 87*5" 97% ; 60" 3%. The corresponding results for the binary systems formed by triphenylmethane with phenols are Phenol 31" 26% ; p-naphthol 77" 80% ; a-naphthol 74" 70% ; catechol 80" 82% ; resorcinol 87" 94%; quinol 91" about 100%; pyrogallol 89" 97.5%; o-nitrophenol 36" 30% ; m-nitrophenol 80" 76% ; p-nitrophenol 86" 92.5%.I n some cases it cannot be decided whether the pure components or saturated mixed crystals of the solid solutions of the two components take part in the eutectic. The latter is prob- able in the systems containing the two naphthols since mixtures at some distance from the eutectic solidify a t temperatures higher than the eutectic temperature. In the systems containing triphenyl- methane and m-(p-)nitrophenol thermal effects occur below the eutectic temperatures namely a t 75" (91") ; for these no explanation is advanced.T. H. P. Preparation of Dihydroxyperylene. ALOIS ZINKE (Brit. Pat. 165771).-One part of 2 2'-dimethoxy-1 1'-dinaphthyl or other alkyl derivative of dihydroxydinaphthyl is heated with 4 parts of aluminium chloride with exclusion of moisture for two hours a t 140-150". The molten mass is treated with hydrochloric acid and the dihydroxyperylene formed is separated and purified by reprecipitation from sodium hydroxide solution or glacial acetic acid in which reagents it is readily soluble with an intense green fluorescence. 1 12-Dihydroxyperylene is also readily soluble in benzene and toluene but sparingly so in alcohol. Its solution in aqueous sodium hydroxide is readily oxidisable to the quinone which however is again reduced on treatment with sodium hypo- sulphite.G. F. M. Preparation of Perylene. ALOIS ZINKE (Brit. Pat. 165770) .- 1 12-Dihydroxyperylene (cf. preceding abstract) is reduced by dist.illing with or over zinc dust or iron powder. For example perylene is obtained as a reddish-yellow oil which after solidifica- tion is purified by crystallisation by distilling a mixture of 1 part of dihydroxyperylene and 2 parts of zinc dust in a current of hydrogen and passing the vapours over heated pumice stone impregnated with zinc. G. F. M. The Reaction between Sulphur Monochloride and Aniline. S. COFFEY (Rec. trav. chim. 1921 40 747-752; cf. Michaelis A. 1891 74 310 and 715).-In attempting to prepare the sulphurORGANIC CHEMISTRY. i. 133 analogue of nitrobenzene by the action of sulphur monochloride on aniline in dilute ethereal solution quantitative reaction takes place according to the equation 3NH2Ph + S,Cl -+ NPhS + 2NH3PhC1 provided the temperature is sufficienhly low.The compound NPhS is a thick red liquid which cannot be distilled or crystallised. Some of its chemical properties are described. The name dithio- phenylamine is suggested in place of thionitrobenzene as the substance is analogous to the thionylamines. The nitrogen-sulphur linking is very unstable. Chlorination and the Formation of Chloroamines by means of Nitrogen Trichloride. GEORGE H. COLEMAN and WILLIAM ALBERT NOYES ( J . Amer. Chem. Xoc. 1921 43 2211-2217).- Nitrogen trichloride reacts with ethyl chloride giving among other products ethylene chloride which is not a normal product of the action of free chlorine on ethyl chloride in the absence of a catalytic agent.With toluene nitrogen chloride gives benzyl chloride and the monochlorotoluenes together with more highly chlorinated derivatives. With benzene the main product is benzene hexachloride. I n addition to the above products toluene benzene and benzyl chloride all give with nitrogen trichloride small amounts of AT-chloroamines the chloroamine group being located in the nucleus in each case and not in the side chain. These chloroamines are then further chlorinated by the nitrogen trichloride or free chlorine. Thus with benzene the ultimate product is probably pentachlorophenyldichloroamine C&&*NC12. These chlorinations take place at the ordinary temperature and hence are not mole- cular rearrangements but similar to the chlorination of aniline hydrochloride by free chlorine. The chlorophenyldichloroamine is decomposed by hydrochloric acid giving chlorine and chloroaniline The action of nitrogen chloride on benzene is considered to be H.J. E. ( 1 ) C6H 6 + NCI = c1( C6H ,)NCI = C6H 'NC1 + HCI (2) NC13+4HC1=3C1,+NH,C1. The free chlorine from the second reaction chlorinates the chloro- amine. The formation of hydrogen chloride in reaction (1) involves a change of positive chlorine to negative and this possibly accounts for the formation of considerable quantities of free nitrogen. W. G. Hydroxybenzyldimethylamine. A. MADINAVEITIA (Anal. F k . &uim. 1921 19 259-264).-Following the method indicated in Bayer's patent (D.R.-P.92309) o-hydroxybenzyldimethylamine OH*C6H,-CH,*NMe2 was prepared by the action of 40% form- aldehyde on a mixture of phenol and aqueous dimethylamine. The reaction is incomplete in the cold but is completed by boiling for three to four hours under a reflux condenser. On cooling the mixture is acidified with hydrochloric acid and extracted with ether to remove excess of phenol. Excess of aqueous ammonia is added and the amine thus liberated is extracted with ether. The ethereal solution is dried with anhydrous sodium sulphate and after removal of the ether by evaporation the residue is fractionated. f VOL. CXXIT. i.i. 134 ABSTRACTS OF CHEMICAL PAPERS. The base%hus obtained has b. p. 105-106"/18 mm.; 1.5273. The picrate crystallises in rosettes m.p. 151". By treatment of the base with acetic anhydride and saponification of the acetate saliretin is obtained. By a similar reaction using guaiacol a compound of formula OH/-\CH,*NMe is obtained ; it is an oil with b. p. 147-148"/15 mm.; the picrate has m. p. 202". By hydrolysis of the diacetate vanillyl alcohol is obtained (cf. Tiffeneau A. 1911 i 775 810). Derivatives of 2 4 6-Trinitrobenzaldehyde. 11. ALES- ANDER LOWY and WILMER BALDWIN ( J . Amer. Chem. SOC. 1921 43 1961-1963).-A continuation of previous work (cf. Lowy and Balz A. 1921 i 337). The following compounds are described. 2 4 6-Trinitrobenxylidene-o-phenetidine m. p. 175.5"; 2 4 6- trinitrobenxylidene-p-phenetidine m. p. 177" ; 2 4 6-trinitroben~yl- idene-o-anisidine m. p. 171.5" ; 2 4 6-trinitrobenxylidene-p-anis- idine m.p. 182"; 2 4 6-trinitrobenxylidene-o-chloroaniline m. p. 187" ; 2 4 6-trinitrobenxylidene-p-chEoroaniline m. p. 180" ; and 2 4 6-trinitrobenxyZidene-2 4-dichloroaniline7 m. p. 198". When the condensations of 2 4 6-trinitrobenzaldehyde with o-chloroaniline p-chloroaniline and 2 4-dichloroaniline were carried out in hot glacial acetic acid solution products were obtained having m. p. in all cases approximately 100" higher than those of the products prepared in the cold solution. These compounds are probably bimolecular condensation products. p-Naphthylmethylamine-6-sulphonic Acid. GILBERT T. MORGAN and HORACE SAMUEL ROOKE ( J . SOC. Chem. Ind. 1920 41 1-3~) .-P-Napht,hylmethylamine- 6-sulphonic acid NHMe*C ,,H G*S O,H,H,P colourless crystals m.p. 292" after becoming changed at 280° is obtained by the action of methylamine hydrochloride and aqueous sodium hydroxide on Schaffer salt a t 180-200". The following salts are described sodium (+ 3H20 and anhydrous) potassium (+ 3H,O and anhydrous) calcium (+ 6H,O and anhydrous) barium (+ 10H20 and anhydrous) zinc (+ 6H,O and anhydrous) magnesium (+6H,O and anhydrous) copper silver and lead. The dyes pro- duced by coupling p-naphthylmethylamine-6-sulphonic a'cid with the diazo-derivatives from aniline p-nitroaniline picramic acid diaminostilbenedisulphonic acid and tolidine are described ; sodium benxeneaxo-p-nuphthylmethylamine-6-sulphonate forms bright red crystals. P - Naphth ylmeth ylnitrosoamine- 6-sulphonic acid SO,H*C,,H,*NMe*NO yellow needles is converted by alcoholic hydrogen chloride into I.-nitroso- p-~phthylmethylamine-6-~u~p~onic acid orange crystals.The latter substance is converted by evapora- tion to dryness of its solution in hydrochloric acid or by treatment with acetic acid and zinc chloride into ap-naphthiminaxole-6-sul- phonic acid SO,H*C,,H,<~~>CH pale yellow needles. Acetyl- f~naphthylmethylnmine-6-5 ulphon yl chloride NMe Ac-C ,,H ,-SO,Cl OMe \-/ G. W. R. W. G.ORGANIC CHEMISTRY. i. 135 crystallises in prismatic needles m. p. 142-143"; it is converted by ethyl alcohol into the corresponding ethyl ester colourless needles m. p. 125-126" and by ammonia into the sulphonamide colourless prismatic needles m. p. 184-185". Benxoyl-p-naphthyl- methylamine-6-sulphonyl chloride forms colourless rhomboidal prisms m.p. 115-116" and the corresponding sulphonamide crystallises in brownish-white plates m. p. 225-226". Sodium ~-napht~hylmethylamine-6-sulphonate is transformed by methyl sulphate in alkaline solution into the quaternary ammonium salt S 03Na*C,oH,*NMe3-S 04Me,4H,0 which is converted by concen- trated aqueous potassium hydroxide solution into potassium ~-naphthyldi~methylamine-6-sulphonate S0,K*C,oH6*NMe2,3H,0. H. W. Freezing-point Diagram of the System Phenol-Water. F. H. RHODES and A. L. MARKLEY ( J . Physical Chem. 1921 25 527-534) .-The complete freezing-point diagram of the system phenol-water has been experimentally determined. It is shown that pure phenol has a melting point of 40*8" a value which is considerably lower than the usually accepted value of 42-43".Phenol forms a definite hydrate 2PhOH,H20 m. p. 15.9". The system consists of stable equilibria between phenol phenol hydrate and water and metastable equilibria between anhydrous phenol and water. Because of the tendency toward suspended transforma- tion the solid phase which ordinarily appears when a mixture of phenol and water is cooled is the metastable anhydrous phenol. Hydrated crystals were obtained only by seeding with the hydrate or by cooling to very low temperatures. Phenol hydrate forms a eutectic with water containing 95% water a t 0.85" and one with phenol containing 8.25% of water a t 15.8". In the metastable region a t 1*7" two liquid phases appear a saturated solution of phenol in water and a saturated solution of water in phenol.J. F. S. The Action of Nitrous Acid on Phenols. H. A. J. SCHOU- TISSEN (Rec. trav. chim. 1921 40 753-762; cf. Nietzki A. 1890 156) .-By a modification of Liebermann's reaction indophenols may be prepared from phenols in one operation. The reaction takes place in two stages first the formation of a nitroso-compound followed by the condensation of this compound with a second molecule of the phenol. The facility with which the second stage takes place depends on the nature of the intermediate nitroso- phenol. The colouring matters formed in these reactions should be classed among the indophenols as only a small proportion is transformed into oxazine derivatives by the closing of the ring. The author criticises the views put forward by Meyer and Elbers (A.1921 i 240). 111. Nitrophenoxides of the Alkali Metals. DOROTHY GOUDARD and ARCHIBALD EDWIN GODDARD (T. 1922,121 54-58). H. J. E. Metallic Derivatives of Nitrophenolic Compounds. f 2i. 136 ABSTRACTS OF CHEMICAL PAPERS. Compound Formation in Phenol-Cresol Mixtures. JAMES KENDALL and J. J. BEAVER ( J . Amer. Chem. Xoc. 1921,43 1853- 1687; cf. this vol. ii 32 33).-Phenol and the three cresols have been exhaustively purified by repeated fractionation and absolute purity determined by a minimum specific conductivity. The follow- ing data are recorded for the pure substances Phenol freezing point 39*70"&0.02" specific conductivity 40" 11.98 x 10-8 and 50" 14 07 x 10-8; o-cresol f. p. 30*60"~0*02" specific conductivity 0.127 x a t 25"; p-cresol f .p. 34.55"&0-02" specific con- ductivity 1.378 x 10-8 a t 25"; m-cresol f. p. 11~10"&0~02 specific conductivity 1.397 x 10-8 a t 25". These values are compared with the best existing data. The specific conductlivity of the six possible binary systems made up from phenol and the cresols has been determined for the whole range of concentrations a t 25". A series of viscosity determinatioiis of these same binary systems is recorded for 25". A series of molecular weight determinations of the pure substances and certain of the mixtures in solutions in benzene have been made by the freezing-point method. The results indicate that without exception no increase in molecular complexity occurs on mixing these substances. This is in complete accordance with the views correlating additive compound forma- tion with diversity in character of the components put forward previously (Zoc.cit.). It is apparently in disagreement however with the fact that Dawson and Mountford (T. 1918 113 923) succeeded in isolating definite compounds from cresol-phenol mixtures in five out of the six systems. It is however shown that the compounds obtained by these authors are to be regarded as substitution rather than as additive compounds. Under this view no conflict exists between the results of Dawson and Mount- ford and those of the present work; both fall directly into line with the general theory. J. F. S. Catalytic Hydrogenation of Polyphenols by the Wet Way. J. B. SENDERENS and J. ABOULENC (Cornpt. rend.1921 173 1366-1367) .-Quinol resorcinol catechol pyrogallol phloro- glucinol and hydroxyquinol can be reduced in alcohol by the action of hydrogen under a pressure of 30-50 kilos. in the presence of reduced nickel a t 115-130" or in aqueous solution a t slightly higher temperatures. At higher temperatures secondary reactions occur. At 130" in alcoholic solution resorcinol gives cyclohexane- 1 3-dio1 but a t 180" cycEohexano1 is the principal product. W. G. Waage's Phytochemical Synthesis of Phloroglucinol from Dextrose. M. NIERENSTEIN (Nature 1920 105 391) .-A series of nearly eighty experiments performed during fifteen years failed to confirm statements based on Waage's observations (A. 1891 605; Ber. deut. bot. Ges. 1890 8 250) that phloroglucinol is formed when leaves floating in solutions of sugar are exposed to sunlight.A. A. E.ORGANIC CHEMISTRY. i. 137 Natural and Artificial Pepper-substances and the Relation between Chemical Constitution and Peppery Taste. ERWIN OTT and KURT ZIMMERMANN (Annalen 1921 425 314-337).- The elucidation of the constitution of capsaicin by Nelson (A 1919 i 543) is made the basis of an examination of the extent to which the various features of the molecule contribute to produce the peppery taste characteristic of that substance. Capsaicin is the vanillylamide of a decenoic acid OH/-\.CH~.NH.CO.C,H~ \-/ OMe and it is known that the vanillylamide of Am-undecenoic acid has a similar and about equally sharp taste. Undecenoic acid is therefore condensed with a number of bases more or less closely related to vanillylamine and it is shown that the p-hydroxybenzyl- amide (m.p. 86") has a taste considerably weaker than that of capsaicin whilst the taste of the o-hydroxybenxylamide (not purified) is weaker still. Hence the presence of the methoxy- group and the particular orientation of the hydroxyl group in capsaicin both contribute to its taste. The presence of a phenolic hydroxyl group appears to be essential since both the anisylamide (white leaflets m. p. 91") and the benxylamide (m. p. 51-52") are tasteless. So also is the p-hydroxyphenylamide (m. p. 107") which shows that the component amine must be of aliphatic With regard to the conditions governing the character of the acid residue it is found that the vanillylamides of Aa-nonenoic acid decenoic acid and Aw-undecenoic acid have tastes of a comparable strength whilst those of M-hexenoic acid and crotonic acid possess much less pungent tastes.The taste of the vanillyl- amide of cinnamic acid (white powder in. p. 138") was also only feebly peppery whilst that of the vanillylamide of oleic acid was ex- ceedingly pungent but of different quality from the tastes of capsaicin and its closer homologues. On the other hand the p-hydroxy- benxylamide of Aa-nonenoic acid tastes more strongly peppery than the corresponding amide of undecenoic acid (see above). These facts show (a) that the positions of the double bond in the acid residue has comparatively little influence on the peppery taste of the capsaicin-like amides (b) that on the other hand the length of the carbon chain is important acids wit'h nine ten or eleven carbon atoms showing the phenomenon in the most marked and characteristic manner.One of the most remarkable facts which emerged from the investigation is the necessity for an unsaturated linking in the acid component. The vanillylamide m. p. 86" of highly purified stearic acid is quite without taste both in the solid state and in concentrated alcoholic solution. Commercially " pure " palmitic acid on the other hand gives a vanillylamide (m. p. 79") which has a sharp taste but this is due to the presence of traces of the oleic acid derivative. When the amide is purified by crystallisation from ether the taste of the solid amide vanishes but it is still type:i. 138 ABSTRACTS OF CHEMICAL PAPERS.intense in alcoholic solution. A very delicate test for unsaturated acids may be based on these results. The piperidide of sorbic acid m. p. 77" has a taste which is very bitter but not a t all peppery. C. K. I. Benzyl Compounds [Benzyl Alcohol]. J. MESSNER (Pharm. Zentralh. 1922 63 l).-The instability of aqueous solutions of benzyl alcohol even in the absence of air as for example when sealed up in ampoules is ascribed to autoxidation catalysed possibly by traces of alkali from the glass resulting in the forma- tion of l mol. of toluene and l mol. of benzaldehyde and water from 2 mols. of the alcohol. A similar change occurs with aqueous solutions of benzyl benzoate which after a week or so acquire a strong odour of benzaldehyde remaining however neutral in reaction.In this case 2 mols. of benzaldehyde are formed by autoxidation of the ester according to the scheme CH,Ph*CO,Ph + 2CHPhO. G. F. M. Influence of Substitution in the Components on Equilibria in Binary Solutions. XXXV. The Binary Systems of Triphenylcarbinol with Pyrogallol Nitrophenols Polynitro- benzenes and Phenylenediamines. ROBERT KREMANN HEINZ HOHL and ROBERT MULLER I1 (Monatsh. 1921 42 199-220; cf. this vol. i 131 159).-Triphenylcarbinol (2 mols.) and pyrogallol (3 mols.) form a compound m. p. 97" giving a t 65" a eutectic with triphenylcarbinol and a t 76" a eutectic with pyrogallol these containing respectively 70 Yo and 49 yo of triphenylcarbinol. The latter forms with 0- and p-nitrophenols eutectics a t 41" and 97" containing 90 yo and 63 yo of the nitrophenol.Triphenylcarbinol and m-nitrophenol form a compound which appears to contain 1 molecule of the former and 2 molecules of the latter component and undergoes considerable dissociation when fused. The system triphenylcarbinol-picric acid forms a compound (1 mol. 1 mol.) m. p. 138*5" which gives with picric acid a t 110" a eutectic con- taining 23% and with triphenylcarbinol at 122" a eutectic con- taining 67 % of triphenylcarbinol. The binary systems formed by triphenylcarbinol with 0- m- and p-dinitrobenzenes 2 4-dinitrotoluene7 and 2 4 6-trinitro- toluene form eutectics a t 102" 82" 132" 65" and 76" respectively corresponding with 67% 82% 64% 88% and 92% of the res- pective nitro-components. The system triphenylcarbinol-trinitro- benzene forms a compound m.p. 134.5" which contains 2 mols. of the alcohol to 3 mols. of the nitro-compound and gives eutectics with the components a t 133" and 112" respectively and corre- sponding with 48 yo and 15 ?& of triphenylcarbinol. Witlh the binary systems formed by triphenylcarbinol with p - and m-phenylenediamines the fusion curves of the components meet in eutectic points a t 118" and 59.5" respectively these corre- sponding with 67% and 10% of triphenylcarbinol. T. H. P.ORGANIC CHEMISTRY. i. 139 The Interaction of Aromatic Disulphides and Sulphuric Acid. SAMUEL SMILES and ERNEST WILSON MCCLELLAND (T. Preparation and Properties of the Benzochloroarnides. GEORGE ROBERT ELLIOTT (T 1922,121 202-209). Steric Hindrance of the Sulpho-acid Group. C. F. VAN DUIN (Rec.trav. chim. 1921 40 724-735).-In preparing the methyl esters of isomeric sulphobenzoic acids the yield is much greater in the case of the ortho-acid whilst in the saponification of these esters the S0,Na-group in the ortho-position considerably retards the reaction. Anomalous results are given by o-sulph- amino-benzoic acid. The conclusions drawn are consistent with those of Remsen and Reid (A 1899 i 507). Azomethine Derivatives of the 2- and 4-Hydroxy-a-Naphth- aldehydes. GILBERT T. MORGAN and HARRY GORDON REEVES Reduction of Naphthalene- and Naphthol-carboxylic Acids. HUGO WEIL and HERMANN OSTERMEIER (Ber. 1921 54 [B] 3217-3219) .-It has been shown previously that salicylic acid is reduced by sodium amalgam in the presence of boric acid to salicylaldehyde in good yield (A.1908 i 800). The observations have now been extended to certain carboxylic acids of naphthalene and the naphthols. Under these conditions cc-naph,thoic acid is almost unaffected whereas p-naphthoic acid is partly converted into p-naphthaldehyde m. p. 60-5-61 O (phenylhydraxone colour- less leaflets m. p. 217-218"). 1-Naphthol-2-carboxylic acid gives the corresponding aldehyde m. p. 59" the yield being 57y9 calculated on the reduced acid. 2-Naphthol-3-carboxylic acid is transformed into an aldehyde C,,H,,O b. p. 12a0/12 mm. (phenyE- hydraxone m. p. 97"). The substance behaves like an aliphatic aldehyde being resinified by alkali and reducing ammoniacal silver solution Fehling's solution and potassium permanganate in cold solution ; i t appears to be tetrahydro-p-naphthaldehyde 1922,121 86-90>.H. J. E. (T. 1922,121 1-7). - - - - CHz-?H*CHo. It gives a bisulphite compound which is !H4%H,-CH freely soluile in Gater. H. w. Carboxylic Acids of the Semibenzene Group. K. v. AUWERS and K. ZIEGLER (Annalen 1921 425 280-294).-This communication shows that the types of transformation previously discussed (A. 1911 i 298) have some degree of generality. Ethyl cc-4-hydroxy-1-methyl-1 -dichloromethyl-A2' '-cyclohexadiene- 4-propionate CO,Et*CHMe*C( OH)<CH:CH>CMe*CHCI CH'CH is obtained as a viscous dark oil (impure) by the action of ethyl cc-bromo- propionate and zinc dust on 1 -methyl- l-dichloromethylcyclo- hexadien-4-one and on hydrolysis by means of cold alcoholic alkali yields the oorresponding acid which forms Stout whitei.140 ABSTRACTS OF CHEMICAL PAPERS. crystals m. p. 123" (decomp.). On shaking with formic acid the ester of the hydroxy-acid is dehydrated forming ethyl a- 1 -methyl- 1 -dichloromethyl-A2 5-cyclohexadien- A4-propionate ( di7'6 1.2033 d;" 1.201 n2'6 1.56017 n:"j 1.56682 n$ 1.5657) which on hydrolysis by means of alcoholic potassium hydroxide yields the free acid a yellow crystalline powder m. p. 101-103" and can be regenerated from the acid by treating its silver salt with ethyl iodide. On heating the acid undergoes isomeric change with the formation of p p-dichloro-a-p-tolylisobutyric acid needles m. p. 135-136" which when treated with alkali is converted into p-chloro- a-p - dimethylstyrene. . 1 3-Dimethyl- 1-dichloromethylcycZohexadien-4-one on condensa- tion with ethyl bromoacetate and zinc yields ethyl a-1 3-dimethyl- 1 - dichloromethyl - AZz5 - cyclohexadien - A4 - acetate (d:7'6 1.2026 d;O 1.200 nk7.6 1.56219 n$"j 1.56898 n; 1,5679).The free acid m. p. 125-126" on heating in petroleum is converted into ~~-dichloro-a-m-4-xyZylpropionic acid m. p. 132-132*5" which on hydrolysis by means of boiling sodium carbonate solution yields p-chloro-2 4-dimethylstyrene. This substance on oxidation in aqueous acetone by permanganate gave 2 . 4-dimethylbenzaldehyde which was identified as its semicarbazone. Ethyl p p-dichloro- a-m-4-xyZylpropionate b . p. 170-1 75" / 16 mm. is best obtained by the action of heat on ethyl cc-1 3-dimethyl- l-dichloromethyl-A2~5-cyclohexadien-A4-acetate. On boiling with alcoholic alkali it is converted into p-chloro-2 4-dimethyylatropic acid C,HbXe2*C(C0,H):CHC1 which crystallises in stout- tablits m.p. 111 . C. K. I. Friedel and Crafts' Reaction. The Preparation of 2-p- Toluoylbenzoic Acid. T. C. MCMULLEN ( J . Amer. Chem. SOC. 1921 43 1965).-In the preparation of 2-p-toluoylbenzoic acid from toluene phthalic anhydride and aluminium chloride good yields of the acid were obtained using 20 grams of toluene 5 grams of the anhydride and 9 grams of the chloride. Increasing the amount of phthalic anhydride or introducing acetic anhydride reduced the yield of acid very considerably or prevented its for- mation but resulted in good yields of ditolyl phthalide (cf. Rubidge and Qua A. 1914 i 539). The Carbomethoxybenzoyl Chlorides with Aromatic Hydrocarbons and Aluminium Chloride.MAURICE E. SMITH ( J . Amer. Chem. SOC. 1921 43 1920-1924) .-The reaction of each of the carbomethoxybenzoyl chlorides with benzene toluene and m-xylene respectively in the presence of aluminium chloride has been studied. In each case the reaction with toluene takes place in the para-position to the methyl group and with m-xylene in the para-position to one of the methyl groups. o-Carbomethoxybenzoyl chloride gave under these conditions with benzene after hydrolysis of the ester o-benzoylbenzoic acid ; with toluene p-toluoyl-o-benzoic acid and with m-xylene 2 4-di- W. G. Friedel and Crafts' Reaction.ORGANIC CHEMISTRY. i. 141 methylbenzoyl-o-benzoic acid. m-Carbomethoxybenzoyl chloride gave with benzene m-benzoylbenzoic acid ; with toluene p-toluoyl- m-benxoic acid m.p. 172" giving a silver salt and a methyl ester m. p. 108" ; and with m-xylene 2 4-dimethylbenxoyl-m-benxoic acid m. p. 168" giving a silver salt and a methyl ester m. p. 73". p-Carbo- methoxybenzoyl chloride gave with benzene p-benzoylbenzoic acid ; with toluene p-toluoyl-p-benzoic acid and with m-xylene 2 4-dimethylbenxoyl-p-benxoic acid m. p. 185" giving a silver salt and a methyZ ester m. p. 59". isoPhthalic and terephthalic acids were readily obtained by the oxidation of commercial xylene with potassium permanganate in the presence of sodium hydroxide the two acids being separated by means of the differing solubilities of their barium salts. W. G. The Friedel and Crafts' Reaction. Bromophthdic Anhy- drides Benzene and Aluminium Chloride.H. N. STEPHENS ( J . Amer. Chem. SOC. 1921 43 1950-1956).-The various o- beiizoylbromobenzoic acids and the diphenylbromophthalides have been prepared and identified. 3-Bromophthalic acid was prepared most satisfactorily from 3-aminophthalic acid by the Sandmeyer reaction. Its anhydride when boiled with benzene and aluminium chloride for four hours gave 6-benzoyl-2-bromobenzoic acid m. p. 231.5" probably identical with the compound 111. p. 219-221" described by Pechmann as o-bromobenzoylbenzoic acid (cf. Ber. 1879 12 2126). Under similar conditions 4-bromophthalic anhydride gave 2-benxoyl-4-bromobenxoic acid m. p. 193" and 6-benzoyl-3-bromobenzoic acid m. p. 172.5" (cf. Kohler Heritage and Burnley A. '1910 i 562). When 3-bromophthalic anhydride is boiled as above with aluminium chloride and benzene and then to the mixture acetic anhydride and more benzene are added and the boiling is con- tinued a compound m.p. 148-150" is obtained which is not however a diphenylbromophthalide. Under similar conditions 4-bromophthalic anhydride gives a mixture of diphenyl-5- bromo- phthulide m. p. 186" and diphenyl-4-bromophthalide m. p. 115- 116". Diphenyl-3-bromophthalide m. p. f31" was obtained from the mixed anhydride m. p. 168.5" of 6- benzoyl-2- bromobenzoic acid and acetic acid. The mixed anhydride m. p. 83-87' of 2-benzoyl-4-bromobenzoic acid and acetic acid and the mixed anhydride of 6-benzoyl-3-brornobeiizoic acid and acetic acid were also prepared. W. G. A New Alkylamine and certain of its Derivatives.HANS DERSIN (Ber. 1921 54 [B] 3158-3162).-Gabriel and Ohle (A 1917 i 565) have described the preparation of amino-alcohols by the action of alkylene oxides on phthalimide and subsequent elimination of the acid group. Since however the alkylene oxides are generally prepared with considerable loss from the halogen- hydrins it appears more advantageous to cause the latter to react directly with potassium phthalimide. This method has been used already for the preparation of p-hydroxy-n-propylamine (Gabriel f*i. 142 ABSTRACTS OF CHEMICAL PAPERS. and Ohle A. 1917 i 563) and two further examples of its employ ment are now given. Hydroxyethylphthalimide C8H40,:N*CH,*CH,*OH m. p. 88-89" is obtained from potassium phthalimide and ethylene chlorohydrin.isoButylene chlorohydrin prepared from chloroacetone or chloro- acetic ester and magnesium methyl bromide (but not iodide) is converted by potassium phthalimide into a-phthulimino- p-hydroxy- p-nwthylpropane OH*CMe,*CH,-N:C,H,O slender colourless needles or leaflets m. p. 106-107". The yield is not very satis- factory. Attempts to prepare the substance from Grignard's reagents and ethyl phtlhaliminoacetate acetonylphthalimide or phthalylglycyl chloride were however fruitless. The phthalyl derivative is hydrolysed by sulphuric acid to isobutaldehyde and a-amino- p- hydrozy- p-methylpropane OH*CMe,*CH,*NH ; the hydro- chloride very hygroscopic colourless needles m. p. 70-72" platini- chloride long very hygroscopic yellow needles m. p. 172" (decomp.) picrate large prismatic crystals m.p. 165-175" according to the manner of heating and aurichloride long yellow needles or prisms of the latter are described. The base is converted by phenylthiocarbimide into N-phenyl-N'-hydroxyisobutylthiocarbamide NHPh*CS*NH*C,H,*OH colourless needles or prisms m. p. 136- 137" which is transformed by fuming hydrochloric acid a t 100" into the isomeric 2-anilino- 5 5-dimet hylt hiaxoline (?Me2*S>C*NHPh colourless prisms m. p. 153-154". p-Chloro-a-amino-p-methyl- propane Jzydrochloride lustrous needles m. p. 183" (decomp.) is obtained together with the chlorohydrin OH*CMc,*CH,Cl when the alkylamine hydrochloride is heated with saturated hydro- chloric acid at 100"; the oily free base smells like glue and yields a picrate long needles or plates in.p. 159". Potassium thiocyanate converts the chloroalkylamine hydrochloride into 2-amino-5 5-dimethylthiazoline (picrate m. p. 103-106"). With benzoyl chloride arid sodium hydroxide the hydrochloride gives @-chloro-cc-benzamido-p-methylpropane CMe,Cl*CH,*NHBz m. p. 97-98" which is transformed by boiling water into 2-phenyl- 5 5-dimelhyloxaxoline a liquid which gives a picrate needles ni. p. 198-199". The pZatinichZoride of the chloroamine CR!te,Cl*CH,*NH crystallises in six-sided prisms m. p. 200". a-Phthalimino-p-hydroxy-P-methylpropane exchanges its hydr- oxyl-group readily for a halogen atom when warmed with halo- gen acids. It thus gives ~-chloro-a-~htJutlimino-~-meth~lpropa~~e CRlae,Cl*CH,=N:C8H,0 needles m. p. SS-S9" the corresponding iodo-compound prisms m.p. 100-lOl" and bromo-derivative needles or leaflets m. p. 97". The latter can be converted by potassium hydroxide acetic acid and nitrous acid into the 12itroso- CH,-N A COON( NO)*C/H CO-O-CMe compound C,H,< needles or prisms in. p. 154" (decomp.). Attempts to cause trirnethylethylenechloroliydrin to rea,ct with potassium phthalimide were unsuccessful. OH*CMe,*CHMeCl H. VS'.ORGANIC CHEMISTRY. i. 143 Synthesis of Inactive Para- and Anti-hydroxyaspartic Acids (Aminomalic Acids) [Aminohydroxysuccinic Acids]. H. D. DAKIN (J. Biol. Chem. 1921 48 273-291).-Attempts to obtain aminohydroxysuccinic acid C0,H*CH(OH)*CH(NH2)*C02H either synthetically or as a degradation product of proteins have not hitherto been successful although its isolation has been incor- rectly reported (Skraup A.1904 i 539 ; Neuberg and Silbermann A. 1905 i 418 ; Lossen A. 1906 798). In view of its possible occur- rence in proteins it was therefore prepared by heating chloromalic acid with 5 parts of concentrated aqueous ammonia for about ten hours in an autoclave immersed in a boiling water-bath. After removal of chlorine it was isolated from the reaction product by means of its lead salt. The acid so obtained forms a syrup which is difficult to crystallise unless seeded and consists of a mixture of two optically inactive isomerides. Separation of these was effected by fractional crystallisation from water. The less soluble isomeride the para-acid forms small opaque cubes decomposes slowly when heated above 235' and is converted by nitrous acid into racemic acid.The more soluble form the anti-acid forms hexagonal plates and thick prisms and gives mesotartaric acid on similar treatment. With phenylcarbimide phenylhydantoin deriv- atives are produced the para-compound forming bunches of white needles m. p. 201-5-202.5" and the anti nacreous plates m. p. 196-198'. The various salts produced have the following composition (Para) (C,H60,N),Ca,5H,0 ; C4H505NCa,Aq ; (C,H605N),Ba,3M20 ; C4H50,NBa ; (C4H,05N),Cu,,8H20 ; (C4H4N0,),Zn,,7H,0. (Anti) (C4H,0N,),Ca,4H,0 ; C4H50N,Ca 2H20 ; (C4H605N),Ba,3H,0 ; C,H,O,NBa ; (C,H40,N)2C~3,8HZ0 ; By heating chloromalic acid with aniline the dianilide of anilino- kydroxymccinic acid CO(NHPh)*CH( NHPh)*CH( OH)*CO (NHPh) nodular clumps of bright yellow needles softening above 200" arid melting a t 210-21 1 O and anilinoh~drox~~llsucci~~ic acid anil (c4H405N).&+j,7N,0.bright yellow plates m. p. 238-239" were CO*$?H*NHPh phN<Co*cHooH obtained . E. S. The Chemistry of Polycyclic Structures in Relation to their Homocyclic Unsaturated Isomerides . 11. Intra- annular Tautomerism. ERNEST HAROLD FARMER CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE (T. 1922,121,128-159). The Direct Acetalisation of Aldehydes. ROBERT DOWNS HAWORTH and ARTHUR LAPWORTH (T. 1922,121 76-85). Catalytic Reduction of' Nitrones. G. CUSMANO (Gaxxetta 1921 51 ii 306-309).-Reduction of an aldonitrone CHR:NR:O by means of the Grignard reagent yields a p-hydroxylamine CH,R*NR*OH (Angeli Alessandri and Ajazzi-Mancini A. 191 1 i 544) whereas the action of nascent hydrogen results in the forma- tion of the Schiff's base CHR:NR.The author finds that catalytic .f * 2i. 144 ABSTRACTS OF CHEMICAL PAPERS. reduction by means of hydrogen in presence of platinum black converts aldo- and keto-nitrones dmost quantitatively into p- substituted hydroxylamines very small proportions of secondary amines being formed in addition. Thus phenyl-N-phenylnitrone yields phenylbenzylhydroxylamine and benzylaniline and the catalytic reduction of anisyl-N-phenylnitrone and dipheny1-N- phenylnitrone proceeds similarly. T. H. P. Chloro- and Bromo-derivatives of Alkylated cgcloHexa- dienones. K. VON AUWERS and K. ZIEGLER (AnnuZen 1921 425 295-313).-1t has been shown (A. 1911 i 383) that the chlorination of 1 -methyl- 1 -dichloromethylcycZohexadien-4-one takes the following course CHC12>C<CHiCCJ.>COy CH'CC1 but that the presence of a methyl group in the '' ortho "-position to the carbonyl group limits the additive power of the molecule Me CHCl CH'CMe CHC12>C <GI€- -CMe>CO -+ M~>c<(cfJ~CH>co * Me CHCl*CHCl CH~~>c~cH~CCl>cO. /CH*CMe - In the present communication it is shown (a) that a methyl group in the meta-position to the carbonyl group does not prevent the addition of the second two atoms of chlorine but nevertheless retards it considerably ( b ) that bromination is governed by the same rules as chlorination.1 2-Dimethyl-l-dichloromethylcycZoliexadien-4-one when treated with chlorine in carbon disulphide takes up two atoms of chlorine with the formation of 5 6-dichloro-1 2-dinzethyZ-l-dichZoromethy.l- A2-cyclohexen-4-one which melts a t 82-83" with evolution of gas and on treatment with potassium acetate in hot acetic acid solution passes smoothly into 5-ch1oro-1 2-dimethyl-1-dichlorornethyl- A2'.'- cyclohexadien-4-one.This substance forms small stout prisms m. p. 101-log" and yields a p-nitrophenyEhydraxone m. p. 206- 208". When however the original ketone is treated in carbon tetrachloride solution with chlorine in sunlight four atoms of chlorine are taken up but the product is too unstable to admit of its being isolated and passes under the conditions of its pro- duction into 3 5-dichloro-1 2-dimethyl-l -dichloromethyZ-A2'5-cyclo- hexudie?a-$-one which forms glistenipg crystals m. p. 87-90' and shows no tendency to condense with p-nitrophenylhydrazine or to combine with chlorine.Lack of tendency to combine with chlorine and p-nitrophenyl- hydrazine is also exhibited by 5-chloro-1 3-dimethyl-1-dichloro- methyl-A2'5-cycZohexadien-4-one and is to be attributed to the presence of two substituents in positions adjacent to the carbonylORGANIC CHEMISTRY. i. 146 group. The same is true of 5-chloro-1 3 6-trimethyl-l-dichloro- methyl- A3 5-cyclohexadien-4-one (m . p . 142-1 43") which is obtained by chlorination of 1 3 6-trimethyl-l-dichloromethyl-A2 :5-cyc10- hexadien-4-one. 5 G-Dibromo- 1 -methyl- 1 -dichloromethyl-Ah3-cyclohexen-4-one7 which when freshly prepared forms colourless needles m. p. 80-81" is obtained by allowing equimolecular quantities of 1 -methyl- 1 - dichloromethyl-Az:"-cycZohexadien-4-one and bromine to combine in carbon disulphide and when boiled with potassium acetate and acetic acid is converted into 5-bromo-1 methyl- l-dichloromethyl- A2:5-cyclohexadien-4-one which has m.p. 89-90" b. p. 183- 185'/15 mm. The p-nitrophenylhydraxone melts a t 154-156". On treatment with magnesium and methyl iodide the ketone is converted into 5-bromo-1 4-dimethyl-1-dich10romethy1-A2~'"-cyc10- hexadien-4-01 which forms slender colourless needles m. p. 103- 104" and is somewhat less stable than its chlorine analogue. 2 3 5 6-Tetrabromo-l-methyl-l-d~c~~loromethylcyclohexan-4-one is obtained in " cis-" and " cis-trans-" modifications by the action of four atoms of bromine on 1 -methyl- 1 -dichloromethyl-A2:5-cyclo- hexadien-4-one.The former crystallises in rosettes of colourless needles m. p. 137" (decomp.) and the latter in needles which immediately after crystallisation melt a t 118-119". This com- pound does not keep well however. When either isomeride or the original crude bromine additive product is boiled with potassium acetate and acetic acid hydrogen bromide is eliminated and 3 5- dibrorno- 1 -methyl- 1 -dichloromet hyl- A2 5-cyclohexadien-4-one is pro- duced. This substance forms prisms or tablets m. p. 120-121" and is stable towards excess of bromine a t 100". It may be pre- pared in small yield by the action of chloroform and sodium hydr- oxide on oo-dibromo-p-cresol and when treated with magnesium and methyl iodide is converted into 3 5-dibromo-1 4-dimethyl-l- dichloromet hyl- A2 :5-cyclohexadien-4 - oZ which crystallises in needles m.p. 91-92' and eliminates water only a t 250". The product of addition of two atoms of bromine to 1 S-dimethyl- l-dichloromethyl-A2~5-cyclohexadien-4-one is too unstable t o admit of its being isolated and passes under the conditions of its forma- tion into 5- bromo- l 3 - dimet h yl- l -dichZoromethyl - A2 5 - cyclohexadien- 4-one7 which has m. p. 65-66' b. p. 180-185'/13 mm. and in agreement with the position assigned to the bromine atom shows no tendency to react with p-nitrophenylhydrazine. C . K. I. The Mutual Replacement of Arnine Residues by Anils. G. REDDELIEN (Ber. 1921 54 [B] 3121-3131).-It has been shown previously (A. 1910 i 118 ; 1913 i 1203) that the formation of ketoneanils can be facilitated greatly by the presence of a suit- able catalyst such as aniline zincichloride or halogen acid but the procedure gives poor yields with many ketones of high molecular weight and substituted anilines by reason of the slowness of the change.The desired anils may however be obtained readily if the simple ketoneanils (in place of the ketones themselves) arei. 146 ABSTRACTS OF CHEMICAL PAPERS. heated with the requisite amine. The process appears to take place in accordance with the scheme R,C:PJPh+H,N.Rl= R,C(NHR1)*NHPh= R2C:NR1 +NH,Ph. The conditions which govern the course of the change are the volatility of the amine the chemical affinity to the ketonic or aldehydic residue and the concentration of the amine. If the eliminated amine is not removed (for example by distillation) an equilibrium governed by the law of mass action becomes established.The replacement of a less by a more volatile amine can however be secured if the latter is used in large excess. The amine residue of ketoneanils can be removed by amino-acids in a similar manner ; the process does not depend on the activity of the carboxyl groups since the fission of ketoneanils by carboxylic acids occurs with much less readiness. The new process can be utilised for the production of ketoneanils which by reason of steric hindrance are not obtainable directly from the ketones the starting point being the ketoneimine. The displacements can be catalytically accelerated by aniline zinci- chloride or halogen acids but this is not generally necessary.The reaction may also be extended to acid amides the same catalysts being operative. Benxophenone-p-nhthil @Ph2:N*C1,H,. short greenish-yellow prisms m. p. 96*5" is prepared by heating a mixture of benzo- phenoneanil and p-naphthylamine ultimately to 180" in a vacuum. Fluorenylidene-p-aminodiphenyl C(C6Hp),:N*C,H4Ph from fluoren- oneanil and p-aminodiphenyl crystalhses in short golden-yellow prisms m. p. 186". Di-or-nuphthylketoneanil from di-a-naphthyl- lcetoneimide m. p. 87" and aniline forms pale yellow prisms m. p. 155". Di-a-nuphthylketone-a-naphthil short yellow prisms has m. p. 21 1". Benxophenone-p-anilinoanil CPh2:N*C6H4*NHPh from benzophenoneanil and p-aminodiphenylamine forms dark yellow oblique four-sided rods m. p. 11 1".Benzophenoneanil-p"-carb- oxylic acid CPh,:N*C,H,*CO,H short pale yellow prisms m. p. 240" is obtained readily from p-aminobenzoic acid and benzo- phenoneanil or benzophenoneimide ; the sodium salt an intensely yellow crystalline powder and the potassium salt are described. Fluorenoneanil-p'-carboxylic acid from fluorenoneanil and p-amino- benzoic acid crystallises in yellow leaflets m. p. 253". Benzo- phenoneimide is prepared conveniently by heating benzophenone- anil a t 200" in the presence of a little aniline hydrobromide in a current of dry ammonia. Fluorenoneimide pale yellow slender needles m. p. 124" is prepared in a similar manner. Benzophenone- methylimide CPh,:NMe a colourless liquid b. p. 158-159"/13 mm. is obtained by heating benzophenoneanil and aniline hydrobromide at 200-210" in a current of dry methylamine.Fluorenonemethyl- imide crystallises in pale yellow leaflets m. p. 110-111". Benxo- phenonebenxoylhydraxone CPh,:N*NHBz from benzophenoneanil and benzoylhydrazine a t loo" forms small colourless rods m. p. 115.5" ; it can also be prepared in almost quantitative yield by protracted ebullition of a solution of its components in alcohol. Fluorenonebenzoylhydraxone forms pale yellow needles m. p. 171". H. W.ORGANIC CHEMISTRY. i. 147 Fission of Anils. G. REDDELIEN and HILDEGARDANILOF (Ber. 1921,54 [ B ] 3132-3142; cf. A. 1910 i 118; 1913 i 1203 and preceding abstract) .-Anils are hydrolysed by aqueous solutions of mineral acids with a readiness which depends to an unusual extent on the presence of substituents.Steric hindrance is shown when the latter are present in the ortho-position but hydrolysis is also facilitated greatly by positive and retarded by negative groups in the para-position. The stability of substances such as benzophenoneanil-p'-carboxylic acid is probably due to a subsidiary valency linking as indicated by the formula CPh,:N*C,H,*CO,H which also renders possible an explanation of the ready fission of the corresponding esters. The anils are much more stable towards alkali than towards acid. The aldehydeanils however are hydro- lysed more or less completely by protracted heating with sodium hydroxide whereas certain ketoanils are completely stable even towards the 300h solution. The similarity of the behaviour of the C:NPh group in anils with the keto-group has been emphasised previously by Miller and Plochl (A.1896 i 609) and by Reddelien (Zoc. c i t . ) . This however does not extend to the behaviour of the substances towards alkali since the ketones undergo fission with much greater readiness than do the ketoanils. The remark- able stability of the latter towards alkali has caused the authors to investigate the possibility of esterifying hydroxyanils and anil- csrboxylic acids and of acylating hydroxyanils and ketoneimides in alkaline solution. Esterification with methyl sulphate proceeds smoothly. Benzoylation according to the Schotten-Baumann method is more complex since the hydroxyanils suffer fission when the solu- tion is warmed whereas in cold solution this action is less marked (but never completely suppressed) and the desired benzoates are produced.Acetylation of hydroxyanils with acetic anhydride and sodium acetate occurs invariably with great smoothness. Benzoylation of the ketoneimines cannot be effected by the Schotten-Baumann method since benzamide is always produced owing to fission of the imine. The benzoylated products can however be prepared in pyridine solution or by the use of benzoic anhydride dissolved in benzene. In contrast to the ketoneimines they are very stable substances which are hydrolysed only by boiling acid or alkali. The anils are also decomposed by hydrogen sulphide in accord- ance with the equation CR2:NPh+H2S=CR2:S+NH2Ph. Reac- tion occurs with some difficulty and not invariably in warm alcoholic solution and is effected preferably by passing hydrogen sulphide through a suspension of the anil salt in benzene.The following individual substances are described. Benzo- phenone-p-dimethylaminoanil CPh,:N*C,H,*NMe yellow crystals m. p. 86-87' which is obtained conveniently from benzophenone dimethyl-p-phenylenediamine and hydrobromic acid a t 160-180" (cf. Reddelien A. 1910 i 118; Moore A. 1910 i 281). Ethyl benxophenoneaniZ-p' -carbox y h t e CPh,:N*C,H,*C02E t (from benzo - phenoneanil and ethyl p-aminobenzoate in a vacuum a t 180-200"),i. 148 ABSTRACTS OF CHEMICAL PAPERS. small yellow needles m. p. 93-94". Methyl benxophemneanil-p'- curboxylate (from the acid methyl sulphate and sodium hydroxide) pale yellow leaflets m. p. 133". Methyl JLEuorenoneanil-p'-carb- oxylate C1,H8:N*C6H4*C02Me yellow leaflets m.p. 170". Ethyl benxylidene-p-aminobenxoate CHPh:N*C,H,*CO,Et pale yellow needles m. p. 47". Benzylidene-p-anisidine m. p. 72". Benxo- phenonebenxoylimide CPh,:N*Bz colourless prisms m. p. 117-1 18". Pluorenonebenxoylimide pale yellow leaflets m. p. 130". Benxyl- idene-p-aminophenyl benzoate CHPh:N*C,H,*OBz colourless needles m. p . 144". The benzoate pale yellow leaflets m. p. 105" and ucetate pale yellow prisms m. p. 93-94" of benzophenone-p-hydroxyanil. Benzilmonoanil is converted by potassium hydroxide a t 170-180" into benzilic and anilinodiphenylacetic acids. Benzophenoneanil hydrochloride is transformed by hydrogen sulphide into thiobenzophenone a dark blue liquid b. p. 176- 178"/18 mm. In a similar manner p-dimethylaminobenxophenone- anil hydrochloride red needles m.p. 178" (decomp.) is converted into p-dimethylaminothiobenzophenone C15H15NS bluish-red rhombic leaflets m. p. 91". Thiobenzophenone is also produced when hydrogen sulphide is passed through molten benzophenoneanil but the action proceeds further to the formation of diphenylmethane CPh,:S+H,S= CH,Ph,+ S,. Under similar conditions fluorenoneanil gives a red sulphide which could not be isolated in a homogeneous condition L " and dithiodifluorenone ~ ~ ~ > C < ~ > C < ~ ~ (cf. Smedley T. 1905 87 1253). H. W. 6 4 Dibenzylideneacetone [Distyryl Ketone] and Triphenyl- methane. X. Ionogenically Linked Halogen Atoms. FRITZ STRAUS and AMADAUS DUTZMANN (J. p r . Chem. 1921 [ii] 103 1-68 ; cf. A. 1912 i 989).-The unsaturated chlorides obtained by the action of phosphorus pentachloride on distyryl ketone and other ketones of similar structure contain the group CHC1 and are derived from diphenylchloromethane by the separation of one of the benzene nuclei from the methane carbon atom by a more or less long conjugated chain of ethylene linkings.In the reactions of these unsaturated chloro-compounds the secondary chlorine atom exhibits a highly developed " ionogenic " linking closely resembling that observed with triphenylchloromethane. Thus the chlorine atom is readily replaceable by hydroxyl methoxyl another halogen etc. and also induces in the compounds ability to unite with com- pounds of different character forming intensely coloured com- plexes. Among the latter a special position is occupied by the additive compounds formed with sulphur dioxide the coloured solutions of these compounds in excess of the liquefied gas exhibiting electrical conductivity ; in a few instances such compounds may be isolated and analysed.The authors have measured the conductivities of a considerable number of these solutions with the object of determining the manner in which the conductivity varies with constitutive altera-ORBAXIC CHEMISTRY. i. 149 tion in the molecular structure of the unsaturated chloro-compounds (cf. Straus and Hussy A. 1909 i 490). Benzyl chloride and diphenylchloromethane which may be regarded as the parent substances of the whole series show no measurable conductivity even in concentrated solution. Conductivity makes its appearance when an ethylene linking is introduced between the methyl carbon atom and the one nucleus and increases with the number of such linkings in the molecule until it assumes considerable magnitude.As regards the influence of nuclear substituents on the conductivity of these unsaturated chloro-compounds the only data available refer to compounds in which either chlorine or methoxyl is intro- duced in the para-position in both nuclei; such data show that the conductivity is diminished by chlorine but is increased by methoxyl to the order of magnitude of the conductivities exhibited by the best-conducting true salts. Thus the influence of nuclear methoxyl suppresses all other constitutive influences. Of the effects on the conductivity of change of the anion little is known.Replacement of the secondary chlorine by bromine results in considerable augmentation of the conductivity. The carbinols obtained by treating the chloro- or bromo-compounds with water also dissolve in liquid sulphur dioxide giving coloured complex compounds the conductivities of which are approximately 10% of those of the corresponding chloro-compounds. The methyl ethers of the carbinols give coloured and conducting solutions in sulphur dioxide only when they correspond with highly conducting chlorides ; the molecular conductivities of such ethers are about one- half as great as those of the corresponding carbinols but persistently increase instead of remaining constant for any definite dilution. The magnitudes of the conductivities of these coloured solutions exhibit parallelism with the intensities of their colour these vary- ing for solutions of the different compounds of similar concentra- tions to the same degree as the molecular conductivities.Indeed in all the cases investigated gradual diminution of the conductivity is accompanied by fading of the colour ; further with the carbinols examined and with triphenylcarbinol which give solutions a t first colourless the subsequent change into coloured solutions corre- sponds with measurable increases in the conductivity. It is there- fore assumed that even in solutions of the chlorides in liquid sulphur dioxide an equilibrium exists between a colourless non- conducting form which may be regarded as formed by hetero- geneous association between molecules of the chloride and of the solvent and represents simple solution such as occurs with organic solvents and a second coloured conducting form arising by transformation of the solvate originally formed XHC1 .. . xS0 (colourless) :CHC1 . . . x S 0 (coloured). With the chlorides themselves the establishment of this equilibrium proceeds too rapidly to permit of direct observation. I n considering the observed variation of the conductivity it must be borne in mind that dilution causes not only the normal increase in the dissociation but also a simultaneous displacement of the equilibrium between colourless and coloured forms.i. 150 ABSTRACTS OF CHEMICAL PAPERS. The results of Hantzsch’s investigations (A. 1918 ii 2 4) show that the process of ionisation does not of itself conditlion alteration of the light absorption and that with a coloured ion there must correspond a coloured non-dissociated parent form.Hence in the coloured solutions of these chlorides in sulphur dioxide the presence of a second coloured ionisable compound must be assumed. As yet it has not been found possible to prove experi- mentally the assumed scission int’o such ions as CPhCl:CH*CPh’ . . . x S 0 and C1’ . . . xSO by electrolysis of one of these chlorides (cf. Schlenk A. 1910 i 236). The investigation of the velocities with which these halogen compounds are decomposed by water (A. 1909 i 490; 1910 i 593; 1912 i 989) yielded results which together with those now obtained indicate that similar alterations in the molecules of the halogen compounds or in other words similar alterations in the affinity demands of the methyl carbon atom influence the velocity of the decomposition by water and the electrical conductivity qualitatively in the same direction.The conclusions drawn by Straus Lutz and Hussy (A. 1910 i 563) regarding the dependence of the stability of the coloured complex compounds formed by various chlorides on the number of unsaturated linkings and on the nature of the substitution in the nucleus are confirmed. According to Werner’s hypothesis the hydrolysis of the complex chlorides results first in a loose union of the water molecule with the chlorine atom this proceeding to varying extents with the different chlorides ; the affinities are then brought into equilibrium by the formation of the carbinol rather than by displacement of an electron R,R,HiC*Cl .. . HOH -f R,R,HiC C1.H OH. S J The phenomena observed with the unsaturated chlorides in solution in sulphur dioxide are discussed in relation to the halo- chromy of the unsaturated ketones and it is found that the con- ductivities of sulphur dioxide solutions of these chlorides are extremely small and bear no relationship to those of the corre- sponding chlorides. Walden (A. 1902 i 536) drew the conclusion that the capacity of these chlorides to undergo electrolytic dissociation is determined principally by the number of radicles united to the carbon atom and that only tertiary compounds exhibit appreciable electrical conductivity. The authors’ results show however that secondary halogen compounds also may display the properties of strong electrolytes.A full description is given of the methods employed in the con- ductivity measurements which have been applied to (I) Deriv- atives of benzophenone and fluorenone diphenylchloromethane ; the chloride of 4 4’-diphenylbenzophenone CCl,(C,H,Ph) ; p p’- dimethoxybenzophenone and the corresponding dichloro-compound CC1,( C,H,*OMe) and monochloro-compound CHC1(C6H4*OMe) ; the chloride of fluorenone. (11) Derivatives of phenyl styrylORGANIC' CHEMISTRY. i. 151 ketone ay-dichloro- ay-diphenylpropylene ; ay -dichloro- ay-di-p- chlorophenylpropylene ; a-chloro-7- bromo-ay-di-p-chlorophenyl- propylene ; p-anisyl p-methoxystyryl ketone ; cry-dichloro-ay-di- p-anisylpropylene ; a-chloro-y-bromo- ay-di-p-anisylpropylene ; ay- dibromo-ay-di-p-anisylpropylene. (111) Derivatives of distyryl ketone and of phenyl cinnamylidenemethyl ketone ye-dichloro- ac-diphenyl-Aau-pentadiene ; y -chloro- aE-diphenyl-Aau-pentadien- E-01 OH*CHPh*CH:CCl*CH:CHPh and its methyl ether ; yc-di- chloro-ccc-di-p-chlorophenyl-Aay-pentadiene ; -pchloro- ac-di-p-chloro- phenyl- Aa?-pentadiene- E-01 C,H,Cl*CH( OH)*CH:CC1*CH:CH*C,H4Cl and its methyl ether ; c-chloro-a€-di-p-chlorophenyl- Aar-penta- diene ; dianisylidenemethyl ketone ; yc-dichloro-ac-di-p-anisyl- Aar-pentadiene ; y-chloro-e-methoxy-ah-di-~-anisyl-Aar-pentadiene. (IV) Derivatives of dicinnamylidenemethyl ketone ; ae-dichloro-ac- diphenyl- Aau-pentadiene ; a-dichloro-at-diphenyl-ayq-nonatetrene ; e-chloro-aL-diphenyl-aycr]-nonatetren-~-ol and its methyl ether.(V) Tridiphenylylchloromet ham. T. H. P. Halochromic Phenomena with Diarylstyrylcarbinols. KARL ZIEGLER (Ber. 1921 54 [B] 3003-3009).-The recent publication of Hess and Weltzien (this vol. i 36) has induced the author to put forward an account of his work in this field. It is based on the hypothesis that the halochromy of the triaryl- carbinols is connected with the possibility of existence of the triarylmethyls and that the cause is to be found in the unsaturated nature of the benzene nucleus. If this is the case it should be possible to replace the latter by unsaturated groups without dis- turbance of the typical properties of the substances. This has been achieved in a number of instances by the aid of the styryl complex. Benzophenone gives with the magnesium compound of p-bromo- styrene a compound which becomes intensely red and then green when treated with concentrated sulphuric acid the colour dis- appearing on addition of water.A similar substance is derived from phenyl p-tolyl ketone but not from acetophenone thus conforming to theory. The compounds have not been isolated in the homogeneous condition. [With KURT Oc~s.]-The Grignard reagent from p-bromostyrene gives with 4 4'-dimethoxybenzophenone in ethereal solution di- p-anisylstyrylcarbinol OH*C( C,H,*OMe),*CK:CHPh which is isolated in the form of its perchlorate a stable dark red powder m. p. about 90". The salt gives a magenta-red solution in acetone or chloro- form which is stable in the cold but rapidly becomes discoloured when warmed.The similar compounds from other diary1 ketones all give magenta-red solutions but the isolation of other crystalline perchlorates has not been effected. 9-Styrylxan- C104\/CH:CHPh thenyZ perchlorate (annexed formula) is obtained similarly from xanthone ; it forms red prisms or C /\/\/\ thin orange-yellow leaflets decomp. 187-189". 1 I I I The substance is remarkably stable. When \/\/\/ boiled with alcohol it is converted into ms- styrylxanthene m. p. 215". 9-StyryZ-1-meth- 0i. 152 ABSTRACTS OF CHEMICAL PAPERS. oxyxanthenyl perchzorate is a stable dark red powder which softens a t 160" and becomes black without melting at 250". 9-Xtyryldi- PP'-mphthoxanthenyl perchlorate is somewhat less stable. H. W. The Beckmann Transformation. JAKOB MEISENHEIMER (Ber.1921 54 [B] 3206-3213).-Two stereoisomeric forms of benzilmonoxime are known and in accordance with the results of Ph*I=;*Bz and Ph*$*Bz H0.N N*OH the Beckmann transformation the formulz have been assigned to the p- and a-forms. It has been assumed that intramolecular reactions take place with greater readiness when the reacting groups are disposed near to one another in space but this has never been proved strictly to be the case. The incidental observation that 3 4 5-triphenylisooxazole is con- verted by chromic acid in glacial acetic acid-solution or by ozone Ph*f *CO*Ph into benzoyl- P- benzilmonoxime Ph*E-E*Ph -+ K*O*C-Ph N-OBz (Meisenheimer this vol. i 176) proves however that the con- figurations assigned previously to the benzilmonoximes are incorrect and that during the Beckmann change the transformation occurs not between vicinal groups but between those placed in the anti- position t o one another.It is hereby assumed that in the opening of a ring only one form can be produced which must contain the developed groups in the vicinal position to one another; the necessary precautions have been taken to prove that the benzoyl- benzilmonoxime is actually the primary product of the fission of 3 4 5-triphenylisooxazole. The new view of the course of the Beckmann change necessitates a redistribution of the formulae among the benzildioximes the a- - Ph=E *gPh p- and y-forms now receiving the configurations H0.N NOOH) Ph*g- OPh p'l'!?-g OPh respectively thus involving N.OHH0.N ' N*OH N*OH the transpositions of the formula assigned previously to the a- and p-forms whilst leaving that of the y-variety unchanged.A review of the literature on the subject shows that the chemical behaviour of the dioximes is in much better accord with the new than with the older formulze. The mechanism of the Beckmann transformation is now ex- plained in the following manner. I n the oximes the radicles attached to the vicinal carbon atom for example the phenyl group of a-benzilmonoxime exert an attraction on the hydroxyl group and thus displace it from its normal position. The residual or partial valency of the nitrogen atom on the side remote from the hydroxy-group is thereby strengthened. In certain circumstances (the best conditions for the Beckmann change) the residual valency becomes so powerful that it attracts the vicinal group attached to the carbon atom to itself.Momentarily therefore a compound with tervalent carbon and quadrivalent nitrogen is pro- X*N*Bz'ORGANIC CHEMISTRY. i. 153 duced. I n the latter the radicle X attached to the nitrogen by oxygen has but little relationship to the nitrogen and is therefore eliminated and naturally becomes attached to the tervalent carbon atom. Triphenylisooxazole dissolved in carbon tetrachloride is con- verted by successive treatment with ozone and water into benzoyl- p-benzilmonoxime m. p. 137-5-138-5' in addition to a little oxalic and benzoic acids. The oxime and benzoic acids are also produced when the isooxazole is oxidised with chromic acid in glacial acetic acid solution but the yields are very small.Benzoyl- p-benzilmonoxime is obtained conveniently by the action of benzoyl chloride on the oxime in the presence of pyridine. Under similar conditions a-benzilmonoxime gives a compound of the expected composition which however is probably ON-dibenzoylisobcnz- amide OBz*CPh:NBz m. p. 95-96' (cf. Werner and Piguet A. 1905 i 66). Benzoyl- p-benzilmonoxime is converted by sodium hydroxide in aqueous alcoholic solution almost quantitatively into the p-oxime and benzoic acid. Under similar conditions the benzoyl compound obtained from the a-oxime gives benzonitrile and benzoic acid. H. W. Condensation Reactions of Formic Acid. ERW. SCHWENK ( J . pr. Chcm. 1921 [ii] 103 103-105).-That the condensation reaction of formic acid with %methylindole (Scholtz A.1913 i 893) is not confined t o such pyrrole derivatives is shown by the behaviour of formic acid in presence of concentrated sulphuric acid towards 3-oxythionaphthen and towards phloroglucinol. I n the first case the product of the reaction is the 3-oxythionaphthen- 1-aldehydethioindogenide m. p. about 270' obtained by Fried- lander and Kielbasinski (A. 1911 i 1021) from 3-oxythionaphthen- 1-aldehyde and acids and by Friedlander and Risse (A. 1914 i 876) by the action of chloroform and an alkali on 3-oxythio- naphthen ; this compound forms an acetyl derivative C1,M1,02S2 m. p. 211'. The action of formic acid on phloroglucinol in presence of sulphuric acid yields an orange pulverulent compound C1,Hl,O possibly H OH OH H2 0 OH o/-\-cH(oH)-/-\oH \-/ \=/ which does not melt a t 300' and a t 150" is converted into the compound Cl,H,,O,.T. H. P. Preparation of Hydroxyanthraquinones from Nitroanthra- quinones. ERW. SCHWENK (J. pr. Chem. 1921 [ii] 103 106- 108) .-The methods which have been suggested for replacing the nitro-groups of nitroanthraquinones by hydroxyl groups give either poor yields or impure products or are tedious to execute. The author finds however that this replacement may be readily effected by prolonged heating of the nitro-compound with potassiumi. 154 ABSTRACTS OF CHEMICAL PAPERS. acetate and acetic acid in an oil-bath a t 170-180". The nitro- group is doubtless replaced first by acetyl but in no instance could the acetyl compound be isolated; the readiness with which the acetyl group is replaced is doubtless related to the difficulty ex- perienced in acetylating the a-hydroxyanthraquinones (Dimroth Friedmann and Kammerer A.1920 i 443). Replacement of nitro-groups by hydroxyls by the action of potassium acetate does not take place in the naphthalene or benzene series; with 3-nitro- phthalic acid a reaction occurs but this has not been investigated. Derivatives of Anthraquinsne. Aliphatic Thioethers Dithioethers and Thioether Sdphonic Acids. E. EMMET REID COLIN M. MACKALL and GEORGE E. MILLER ( J . Amer. Chem. SOC. 1921 43 2104-21 17).-A4nthraquinone-a-sulphonic acid and the 1 5- and 1 8-disulphonic acids when heated with aliphatic mereaptans in alkaline solution reacted readily to form thioethers thioether sulphonic acids and dithioethers. The reaction takes place rapidly at 100".The corresponding sulphones were pre- pared from the thioethers and dithioethers by oxidation with nitric acid. Thioethers C,,H,O,*SR Anthraquinone methyl thioether m. p. 221"; anthraquinone ethyl thioether m. p. 184"; anthra- quinone propyl thioether m. p. 151" ; anthraquinone butyl thioether m. p. 112.5" ; anthraquinone isobutyl thioether m. p. 141" ; anthra- quinone isoamyl thioether m. p. 86". The corresponding sulphones ClaH70,*S0,R are methyl m. p. 254"; ethyl m. p. 211.5"; propyl m. p. 204.5"; butyl 150"; isobutyl m. p. 190"; isoamyl m. p. 133". The anthraquinone-5-sulphoiiic acid 1-alkyl thiocthers 1 were isolated in the form of various salts as follows T. H. P. The following compounds are described 0 SR /\/\/\ I J SO,Na 0 Anthrayuinone-5-sulphonic acid 1 methyl thioether as its sodium barium aniline m.p. 290-299" (decomp.) o-toluidine m. p. 285- 290" (decomp.) and p-toluidinc m. p. 295-304" (decomp.) salts. A nthraquinone-5-szclphonic acid 1 -ethyl thioether as its sodium barium aniline m. p. 276-286" (decomp.) o-toluidine m. p. 264- 274" (decomp.) and p-toluidine m. p. 276-285" (decomp.) salts. Anthrayuinone-5-sulphonic acid 1 -propyl thioether as its sodium barium aniline m. p. 270-277" (decomp.) 0-tolzcidine m. p. 255- 257" (decomp.) and p-toluidine salts. ,4nthraqui~zone-5-sulphonic acid 1 -butyl thioether as its sodium barium strontium calcium aniline m. p. 257-259" (decornp.) o-toluidine m. p. 234-237" (decornp.) and p-toluidine m. p. 256-260" (decomp.) salts. Anthraquinone-5-sulphonic acid 1 -isoamyl thioether as its sodium barium aniline m.p. 263-265" (decornp.) o-toluidine m. p. 250- 254" (decornp.) and p-toluidine m. p. 267-277" (decomp.) salts. 1 5-dnthraquinone dialkyl dithiocthers dimethyl ; nzethyl ethyl J \,/\/\/ORGANIC CHEMISTRY. i. 155 m. p. 229"; methyl propyl m. p. 209"; methyl butyl m. p. 173.5"; methyl isoamyl m. p. 175"; diethyl m. p. 226.5"; ethyl propyl m. p. 188-5"; ethyl butyl m. p. 156"; ethyl isoamyl m. p. 152"; dipropyl m. p. 227" ; propyl butyl m. p. 175" ; dibutyl m. p. 159.5" ; butyl isoamyl m. p. 134" and di-isoamyl m. p. 158.5". The corre- sponding disulphones are dimethyl ; methyl ethyl m. p. > 300" ; methyl propyl m. p. 291"; methyl butyl m. p. 264"; methyl isoamyl m. p. 266"; diethyl m.p. 269.5"; ethyl propyl m. p. 243.5"; ethyl butyl m. p. 194" ; ethyl isoamyl m. p. 198" ; dipropyl m. p. 265"; propyl bzctyl m. p. 220" ; dibutyl m. p. 184.5" ; butyl isoamyl m. p. 203.5" and diisoamyl m. p. 202". The anthraquinone-8-sulphonic acid 1-alkyl thioethers prepared are as follows 1-methyl as its sodium barium aniline m. p. 260" (decornp.) o-toluidine m. p. 255" (decomp.) and p-toluidine m. p. 260" (decomp.) salts; 1-ethyl as its sodium barium aniline m. p. 250" (decornp.) o-toluidine m. p. 260" (decomp.) and p-toluidine m. p. 255" salts; 1-propyl as its sodium barium aniline m. p. 242" (decornp.) o-toluidine m. p. 260" (decornp) and p-toluidine m. p. 260" (decomp.) salts ; 1-butyl as its sodium barium strontium calcium lead nickel cobalt copper aniline m.p. 260" (decomp.) o-toluidine m. p. 260" (decomp.) and p-toluidine m. p. 255" (de- camp.) salts; and 1-isoamyl as its sodium and barium salts. The 1 8-anthraquinone dialkyl dithioethers are dimethyl m. p. 222"; methyl ethyl m. p. 210"; methyl propyl m. p. 173.5"; methyl butyl m. p. 134" ; methyl isoamyl m. p. 114" ; diethyl m. p. 167.5"; ethyl butyl m. p. 95"; dipropyl m. p. 142"; propyl butyl m. p. 119.6"; propyl isoamyl m. p. 104"; dibutyl m. p. 131"; butyl isobutyl m. p. 103.5"; butyl isoamyl m. p. 116.5" and di- isoamyl m. p. 133". The corresponding disulphones are dimethyl in. p. 310"; methyl ethyll m. p. 220"; methyl propyl m. p. 211"; methyl butyl m. p. 169"; methyl isoumyl m. p. 172"; diethyl m. p. 228"; ethyl butyl 128"; dipropyZ m. p. 210"; propyl butyl m.p. 200.5"; propyl isoamyl m. p. 147.5"; dibutyl m. p. 138"; butyl isobutgl m. p. 168.5" ; butyl isoamyl m. I). 154" and diisoanzyl m. p. 176". Attempts were made to prepare similar derivatives from sodium naphthalene-a-sulphonate but no reaction took place. Preliminary experiments showed that when sodium anthraquinone- a-sulphonate was replaced by the P-sulphonate replacement by the mercaptan residue took place with much greater difficulty if at all. W. G. Boric Esters of Hydroxyanthraqyinones. OTTO DIMROTH and THEO FAUST (Ber. 1921 54 [B] 3020-3034).-Boric acid is used extensively in the chemistry of the hydroxyanthraquinones as a protective agent in oxidations and as accelerator in condens- ations and nitrations. I t s action has been attributed frequently to the formation of boric esters but the question does not appear to have been investigated systematically.It is now shown that boric esters of the hydroxyanthraquinones can he obtained con- veniently from the latter by the action of a solution of boric acidi. 156 ABSTRACTS OF CHEMICAL PAPERS. in acetic anhydride. Thus 1-hydroxyanthraquinone is trans- formed into 1 -hydroxyanthraquinonyl boroacetate which loses a molecule of acetic anhydride when heated in a vacuum and forms 1 - hy drox yant hraquinon yl met a borat e C 14H O,*O*B 0. 2-HydroxyanthraquinoneY on the other hand does not react with boric acid. This difference between the behaviour of hydroxy- groups in positions 1 and 2 is characteristic and general. The unusual greater reactivity of the 1 -hydroxy-group is explained by the hypothesis that a subsidiary valency union occurs between the boron atom and the ketonic oxygen atom thus giving rise to com- pounds of the type indicated by the annexed B(OAc) formula which are thus analogous to the com- pounds with tin tetrachloride described by Pfeiff er (A.3 1913 i 879). The correctness of this sup- /\2\/\ position is supported by the observations that I I 1 I anthraquinone itself reacts with boroacetic anhydr- \,/\(\/ ide (the compound formed could not be isolated) that 1 5-dihydroxyanthraquinone reacts with two molecules of boroacetic anhydride whereas 0 the 1 8-compound reacts with only one molecule and that 1 4 5trihydroxyanthraquinone unites with two molecules of boric acid whilst the third hydroxy-group becomes acetylated. The formation of boric esters of hydroxyanthraquinones in acetic acid solution is accompanied by characteristic changes in colour and spectrum.Investigation of the latter is not yet complete but it is established that all diborates are distinguished by very sharp and characteristic absorption bands. It is remarkable that an x-hydroxy-group in 1 8-dihydroxyanthra- quinone is acetylated readily by warming for a short time with boric acid-acetic anhydride solution whereas such groups are generally difficult to acetylate. I n acetic anhydride solution it is found that 1 8-dihydroxyanthraquinone is more readily mono-acetylated than the 1 5-compound. In general the author is inclined to attribute the difficulty of acetylating and alkylating 0-hydroxy- ketones to chemical rather than to steric effects and suggests the possibility of an unstable subsidiary valency bond between the hydrogen of the hydroxyl group and the ketonic oxygen atom.The analysis of the hydroxyanthraquinonyl boroacetates is effected by decomposing them with water and weighing the pre- cipitated hydroxyanthraquinone. Acetic acid is estimated in the filtrate by titration with alkali until neutral red becomes yellow after which mannitol and phenolphthalein are added and the titration is continued until the solution becomes pink. 1-Hydroxyanthraquinonyl boroacetate orange-red plates which decomposes when heated without showing a definite melting point is prepared by gently warming 1-hydroxyanthraquinone with a solution of boroacetic anhydride in an excess of acetic anhydride ; it is very readily hydrolysed by water and is unstable towards moist air.It loses acetic anhydride when preserved in a desiccator rapidly when heated in a vacuum and passes into 1-hydroxyanthra- C,*H?O,*O*B (OAc) ,-.\ 0 0ORGANIC CHEMISTRY. i. 157 quinonyl metaborate brown crystals which are much more stable towards water than is the boroacetate. 1 4-Dihydroxyanthra- quinonyl diboroacetate forms coarse ruby-red crystals whilst the corresponding di-metaborate is rust-brown. Alizarin 1- boroacetate forms dark red crystals which are extremely sensitive to moisture. 2-Acetylalimrin- 1 -boroacetate orange-red crystals is decomposed by water into 2-acetylalizarin m. p. 198" acetic acid and boric acid. Purpuren- 1 4-diboroacetate purple-red crystals and 2-acetylpur- puren 1 4-diboroacetate dark red to violet-red crystals are also described. Anthrarujindiboroacetate crystallises in golden-yellow iridescent leaflets. Chrysaxin-monoboroacetate pale B(OAc) red crystals with a dull golden glance and ,a'\ 8-acetylchrysaxin-1-boroacetate red crystals are 0 0 described; the latter when hydrolysed gives /\ 2\/\ 1 - h ydroxy -6 -acetox yanthraquinone orange- yellow I I J J prisms m.p. 178" or lemon-yellow needles m. p. \/\/\/ 179" (the two modifications are interconvertible). i> 6 O A ~ 4-Acetoxy-l 5-dihydroxyanthraquinonyl diboroacet- ate (annexed formula) rust-brown crystals with golden glance is hydrolysed by water to 1 5-di- hydroxy -4-acetox yanthraquinone yellow needles m.p. 165"; the position of the hydroxy-groups in the latter follows from its inability to be oxidised by lead tetra-acetate to a di-quinone. H. W. VII. Cobaltic Lakes of the Alizarin Series. GILBERT T. MORGAN and J. D. MAIN SMITH (T. 1922,121 160-169). \/" B(oAc)2 Researches on Residual Affinity and Co-ordination. The Action of Bromine on Quinizarin and Alizarin. OTTO DIMROTH ERNST SCHULTZE and FRITZ HEINZE (Ber. 1921 54 3035-3050; cf. A. 1916 i 563; 1920 i 443).-Quinizarin is unaffected by bromine water a t the ordinary temperature but it is rapidly oxidised by a concentrated solution of bromine in potassium bromide t o quinizarinquinone which is a much more powerful oxidising agent than benzoquinone. Bromine water in presence of free bromine however converts quinizarin into quinixarinquinone dibromide slender pink needles .m.. p. 210- 215" (decomp.) ; this is also formed by boiling quinizarinquinone with an excess of bromine and glacial acetic acid. It is reduced by sulphurous acid to monobromoquinizarin red needles m. p. 228-230" (Liebermann and Riiber A. 1900 i 451) which forms a diacetyZ derivative pale yellow needles m. p. 216-218" whereas treatment with acetic anhydride-sulphuric acid yields dibromo- diacetylquinixnrin pale yellow needles m. p. 270-271" which is hydrolysed by sulphuric acid t o dibromoquinizarin m. p. 252- 253" (Liebermann and Riiber loc. cit.). Quinizarin in methyl alcoholic suspension readily reacts with bromine with ice cooling forming quinixarinquinone methoxy- bromide yellow crystals m.p. 96" which is converted by acetic anhydride in the cold into 3- bromodiacetylpur~urin 2-methyl ether,i. 158 ABSTRACTS OF CHEMICAL PAPERS. pale yellow crystals m. p. 145" hydrolysed by sulphuric acid to 3-bromopurpurin-2-methyl ether red needles m. p. 260". Alizarin reacts with bromine more readily than does quinizarin and forms 3-bromoalixarin yellow plates m. p. 260-261" when boiled with an acetic acid solution of bromine but treatment with bromine water or a potassium bromide solution of bromine or bromine water and free bromine yields in each case 3-bromoalixarin- quinone very sparingly soluble yellow needles which readily decompose. Alixarinquinone methoxybrornide obtained in a similar manner to the corresponding quinizarin derivative forms lanceolate yellow needles m.p. 230" after decomposing and sintering a t 200". A methyl-alcoholic suspension of alizarin on fhe other hand when treated with bromine without cooling yields 3 4-dibromoaEizarirc yellow needles m. p. 251-252" ; diacetyl derivative pale yellow rosettes of needles m. p. 199-200" ; 3 4-dibromoalixarinquinone yellow crystals. Alizarin in ethyl alcoholic suspension reacts with bromine with cooling with formation of alixarinquinone ethoxybromide yellow tables m. p. 205" with decomp. after sintering a t 180". F. M. R. Anthradiquinones and Anthratriquinones . OTTO DIMROTH and VALENTIN HILCKEN (Ber. 1921 54 3050-3063; cf. A. 1916 i 563 ; 1920 i 443).-Quinizarinquinone in glacial acetic acid suspension reacts with hydrogen fluoride with formation of 2-$uoroquinixarin red prisms ; diacetyl derivative slender yellow needles m.p. 189". With benzenesulphinic acid quinizarin- quinone yields quinixarin-2-phenyl~ulphone slender red needles m. p. 250"; diacetyl derivative yellow crystals m. p. 210". When quinizarinquinone is suspended in acetaldehyde and exposed to sunlight in a closed vessel monoacetylquinixarin yellowish-orange needles m. p. 186" is formed. I n order to determine the effect of hydroxyl groups on the properties mono- and di-hydroxyanthradiquinones have been prepared by the oxidation of tri- and tetra- hydroxyanthraquinones respectively with lead tetra-acetate. 6-Hydroxyquinixarinquinone forms small brownish-yellow crystals m. p. 215-220" after decomposing and sintering a t 200" and when treated with acetic anhydride-sulphuric acid yields a mixture of hydroxyanthrapur- purin and hydroxyflavopurpurin. 5-Hydroxyquinixarinquinone forms brown needles m.p. 220" after darkening a t 210". 5 8- Dihydroxyquinixarinquinolze could not be isolated from its deep bluish-violet solution in nitrobenzene. The acetyl derivative of 1 4 5 6 8-pentahydroxyanthra- quinone is obtained by oxidising a glacial acetic acid solution of alizarin- bordeaux with lead tetra-acetate and adding an excess of acetic anhydride and sulphuric acid and similarly the diquinones derived from p-monoacetyl-alizarin-bordeaux and anthrapurpurin were only obtained in acetic acid solution. When 1 2 4 5 8-pentahydroxyanthraquinone and 1 2 4 5 6 8- hexahydroxyanthraquinone are oxidised by air in alkaline solution,ORGANIC CHEMISTRY.i. 159 the tri- and tetra-hydroxyanthradiquinones respectively are obtained and crystallise from aqueous pyridine in dark violet needles. The hydroxy-derivatives of quinizarinquinone are weaker oxidis- ing agents than the parent substance and the oxidising power varies with the position of the hydroxyl group in the molecule for 5-hydroxyquinizarinquinone is a weaker oxidising agent than its 6-hydroxy-isomeride. With regard to the rate of oxidation of a hydroxyanthraquinone to a diquinone the oxidation to an o-quinone proceeds more rapidly than the oxidation to a p-quinone. When an acetic acid or nitrobenzene solution of a polyhydroxy- anthraquinone which contaiiis hydroxyl groups in an ortho- or para-position in both benzene rings is oxidised with lead tetra- acetate the blue to bluish-violet diquinone is first formed but on further oxidation yellow or yellowish-brown solutions of the triquinone are obtained.Solutions of the triquinones derived from 1 4 5 8-tetrahydroxy- 1 2 5 8-tetrahydroxy- pentahydroxy- and hexahydroxy-anthrayuinones were obtained in this manner but the triquinones were not isolated. P. M. R. Influence of Substitution in the Components on Equilibria in Binary Solutions. XXXHI. The Binary Systems o€ Camphor with Phenols. ROBERT KREMANN and FRIEDRICH ODELGA (Monatsh. 1921 42 147-165; cf. this vol. i 131).- The fusion diagrams of the binary systems formed by camphor witlh p - and m-nitrophenols are completely analogous to that of the system camphor-phenol (Kremann Wischo and Paul A.1916 i 217) the curves for the two components falling so steeply that meeting in a simple eutectic is not to be expected; in the region corresponding with 59-69 yo (for p-nitrophenol) or 60- 69 yo (for m-nitrophenol) of camphor no crystallisation is induced by inoculation either with one of the components or with the resorcinol-camphor compound. In almost all cases in which m- and p-nitrophenols form compounds with a second component o-nitrophenol fails to do so owing to steric hindrance. Hence if the inability of the camphor-m-(or p-)nitrophenol system to exhibit crystallisation over the ranges mentioned is due to the existence of a compound seeding with which is impossible the system camphor-0-nitrophenol should form no compound and its fusion diagram should be realisable completely; this is actually the case the eutectic corresponding with 15" and 54% of camphor.The binary systems formed by camphor with 2 4-dinitrophenol and picric acid show similar behaviour the eutectics corresponding respectively with 67" and 61% of camphor and 71" and 60% of camphor ; the 2 4-dinitrophenol and picric acid branches exhibit points of inflexion. Here then unlike what is observed in other analogous cases introduction of electronegative nitro-groups into a compound removes the tendency to combine with camphor. For the systems formed by camphor with pyrogallol and catechol the fusion curves for the two components descend rapidly and do not meet in a eutectic point on extrapolation. If however the intermediate critical viscous melt is seeded with the camphor-i.160 ABSTRACTS OF CHEMICAL PAPERS. resorcinol compound a new branch of the diagram of state is realised this corresponding with the primary crystallisation of a compound of the two components. Contrary to the statements of Efremov (A. 1913 i 635) the compounds formed are composed of 1 moI. of catechol + 2 mols. of camphor and apparently 1 mol. of pyrogallol + 3 mols. of camphor. That the number of mole- cules of camphor combined should agree with the number of hydroxyl groups in the molecule of the other component is con- ceivable but with other compounds such as amines steric hindrance to the valency relations results from t'he ortho-positions of the hydroxyl groups of catechol and pyrogallol so that the number of molecules of the second component combined is usually less than the number of hydroxyl groups in the hydroxybenzene; in such cases the two hydroxyl groups act only when they occur in the meta- or para-position.In their behaviour towards camphor however the valency activities of the hydroxyls of the dihydroxy- benzenes appear to support one another when near and to weaken one another when distant. The fusion curve for the system camphor-quinol exhibits no indication of the formation of the equimolecular compound mentioned by Efremov (Zoc. cit.) . T. H. P. Saponins. V. Hederin and its Hederagenin. A. W. VAN DER HAAR (Ber. 1921 54 [B] 314-2-3148; cf. A. 1916 i 41).- It has been shown previously that the crystalline a-hederin is hydrolysed to a-hederagenin Z-arabinose and rhamnose according to the scheme C,,H + 3H,O = C31M5004+ C5H100 + C6H1,O5.The previous conclusion that it contains five hydroxyl-groups is somewhat modified since four of these are found to be capable of acetylation whereas the fifth is present in the carbosyl group. Since a-hederagenin does not dissolve in aqueous carbonate or bicarbonate solutions whilst it can be titrated with alkali hydroxide in alcoholic solut,ion i t was considered to be a lactone; this view is now abandoned since the methyl and ethyl esters are found to contain the two hydroxyl groups present in the original substance which is now regarded as a dihydroxy-carboxylic acid a-Hederin is converted by diazomethane into the corresponding methyl ester colourless crystals m.p. 198-200" which is trans- formed by acetic anhydride and anhydrous sodium acetate into the tetra-acetyl ester. The sodium salt of a-hederin C,,H6,011Na,5H,0 and the potassium salt are described. Saponins. VI. Hederagenin. A. W. VAN DER HAAR and A. TAMBURELLO (Ber. 1921 54 [B] 3148-3158; cf. van der Haar A. 1916 i 41 and preceding abstract; Palazzo and Tam- burello Arch. Farm. Xci. afi. 1913 5 15).-New analyses of hederagenin have confirmed the formula C,lH,oO proposed by van der Haar. Diacetylhederagenin loses one of its acetyl groups when heated a t 100" or when crystallised from aqueous alcohol and passes into monoacetylhederagenin m. p. 156'. The labile C,H,,(OH),*CO,H. H. W.ORQANIC CEEMISTRY. i. 161 acetyl group appears to be vicinal to the carboxyl-group and to be influenced by its proximity since the di-acetates of the corre- sponding methyl and ethyl esters are completely stable towards aqueous alcohol.The sodium salt of hederagenin C,H ( OH)&02Na H20 is described. Hederagenin methyl ester C,,H,,O4 (from the sodium salt and methyl iodide by the successive action of thionyl chloride and boiling methyl alcohol on the sodium salt by means of methyl sulphate or by diazomethane) has m. p. 240" [a]:" +70.9" in chloro- form solution. Diacet ylhederagenin me thy1 ester C,,H,,O ,,H,O has m. p. 193" [a] +61*8" when dissolved in absolute alcohol. Hederagenin ethyl ester crystallises in small colourless needles m. p. 218-219" [a]g +72.5" in absolute alcoholic solution; the corresponding di-acet'ate has m. p.150" [a] +76*47" when dissolved in chloroform. Hederagenin methyl ester is converted by fuming nitric acid into a nitro-compound decomp. 165" which has not been analysed. The gradual addition of a solution of bromine in chloroform to hederagenin methyl ester dissolved in the same solvent leads to the formation of the dibromo-compound C32H5P04Br2 small colourless needles decomp. 215-217". Bromination of hederagenin under similar conditions appears. to proceed somewhat irregularly giving on the one hand a bromo- derivative colourless needles decomp. 157-158" which was not analysed but is probably a dibromo-compound (Tamburello) and on the other a mixture of two bromo-derivatives lustrous hexagonal leaflets m. p. 242" and pale yellow needles C31H4S04BrZ m. p. 262" (van der Haar); attempts to repeat the latter prepara- tions led however to somewhat different results giving products of m.p. 268-270" and 255" respectively. Hederagenin acid amide C,,H,,O,N,H,O colourless needles m. p. 285" is prepared by the action of ammonia on an ethereal solution of the corresponding chloride obtained by the action of thionyl chloride on hederagenin or its sodium salt. H. W. Picrotoxin. XII. Picrotin Ketone C1,Hl6O3. PAUL HORR- MANN and FRIEDRICH BISCHOF (Arch. Pharm. 1921 259 165- 176).-The ketone C1,H1,O first noticed among the reduction products of picrotoxin by phosphorus and hydriodic acid by Angelic0 (A. 1910 i 577) was obtained in better yield by first converting the picrotoxin into ct-picrotinic acid and picrotoxinic acid by boiling with mineral acid and then reducing these acids in the same way as picrotoxin itself.It was isolated by means of its oxime m. p. 212" and purified by distillation in a vacuum b. p. 190°/S mm. It forms a thick colourless syrup which crystal- lises after long keeping. Its semicarbaxone has m. p. 216". By the action of methyl alcoholic potassium hydroxide it is hydrolysed into acetic acid and the substance C,,H,,O,. An attempted degradation of the ketone by converting it into an unsaturated compound through the corresponding tertiary alcohol obtained by the action of magnesium methyl iodide was not successful. Oximinopicrotin ketone CllHllO,*C(NOH)*COMe is obtained by thei. 162 ABSTRACTS OF CHEMICAL PAPERS. action of amyl nitrite and sodium ethoxide on the ketone.It is a white substance m. p. 215" and forms a semicarbazone m. p. 249" (decomp.) a phenylhydruxone m. p. 220" an oxime m. p. 192" and a benzoyl derivative m.. p. 178-182". It did not yield the diketone on treatment with sodium nitrite or mineral acids but on oxidation with nitric acid or ammoniacal silver oxide it was converted into acetic acid and a inonobusic acid C,,~,,O,*CO,H which could not be obtained in a crystalline condition. By the action of sodium hypobromite the ketone was converted into a-bromopicrotin ketone C,,H,,O,Br coarse needles m. p. 145". G. F. M. Physiology of Anthocyanin and Chemistry of Chlorophyll. J. COSTANTIN (,4nn. Xci. Nut. Bot. 1919 [XI 1 38-52).-A dis- cussion of the present state of knowledge with regard to antho- cyanin and chlorophyll.Reduction with nascent hydrogen of a yellow flavone pigment from Vitis is known to yield anthocyanin and the production of a yellow flavone by oxidation of anthocyanin is affirmed. Chlorophyll is now considered to have the formula CO,H*C,,H,,N,Mg(CO,Me) (CO2*C,,H3,). Treatment with ethyl alcohol produces substitution of an ethyl group for the phytol group yielding Willstiitter's crystallisable chlorophyll. CHEMICAL ABSTRACTS. Catechutannins. I. Paullinia Tannin. MAXIMILIAN NIERENSTEIN (T. 1922,121 23-28). hthracoumarin Derivatives. I. W. J. MINAEFF and KURT RPPER (Momtsh. 1921 42 73-81).-The only derivatives of anthracoumarin (Kostanecki A. 1888 291) as yet known are styrogallol (Jakobson and Julius A. 1888 56 ; Mostanecki A. 1888 292) and a hydroxystyrogallol (Slama A.1900 i 177) which are both mordant dyestuffs. In order to obtain compounds with structures similar to those of the vat dyestuffs derived from anthraquinone the authors have synthesised 6-chloroanthra- coumarin which has been converted into 1 -anilinoanthracoumarin. Preliminary experiments on the preparation of di-anthracoumaryl have also been carried out. The 6-chloro-3-hydroxybenzoic acid required was prepared (1) by Mazzara and Bertozzi's method ( A . 1900 i 596) (2) by Peratoner and Condorelli's method (A. 1898 i 642) with the difference that the hydroxyl of the 6-chloro-3-hydroxytoluene was protected during the oxidation by formation of the mono- phosphoric ester (Heymann and Koenigs A. 1887 241) and (3) by reduction of 6-chloro-3-nitrobenzoic acid (Holleman and de Bruyn A 1901 i 591) followed by replacement of the resulting amino-group by hydroxyl.Condensation of cinnamic and 6-chloro-3-hydroxybenzoic acids in presence of sulphuric acid yields 1 -chloroanthracoumarin which resembles l-chloroanthraquinone in chemical behaviour except that its chlorine is more mobile probably owing to the influence of the negative radicle in the para-position.ORGAN TC CHEMISTRY. i. 163 co 6-Chloroanthracoumarin (annexed formula) sub- limes in long golden needles and crystallises in a 6-Anilinoanthracoumarin C2,H1,0,N prepared /\/'\)\ from 1 -chloroanthracoumarin and aniline in 1 1 I J presence of fused potassium acetate and copper \/\~o'\,/ acetate crystallises in reddish-violet leaflets m. p. The interaction of 6-chloroanthracoumarin and nitrobenzene in presence of " Naturkupfer C " appears to yield di-anthracoumaryl but no pure product was isolated.Phenylthioxanthyl. M. GOMBERG and WESLEY MINNIS (J. Amer. Chem. SOC. 1921 43 1940-1944).-The work of Gomberg and Schoepfle (cf. -4. 1917 i 551) on the molecular weight of phenylxanthyl checked by parallel oxygen absorptions has been extended to phenylthioxanthyl. Pure phenylthioxanthenol chloride was prepared by bubbling dry air through a solution of phenylquinothioxanthenol chloride hydrochloride in dry benzene a t 90". This material was used for the oxygen absorption and for the attempts to prepare the free radicle. The free radicle was prepared in solution but found to be very unstable and it could not be isolated in the solid state.The values obtained by Schlenck and Renning (cf. A. 1913 i 34) for the molecular weight of this substance were made on material which was in all probability not the free radicle. W. G. /\ HS 0 felted mass of golden needles m. p. 274". C1 184-186". T. H. P. 2 2'-Sulphonidotriphenylmethyl. M. GOMBERG and E. C. BRITTON ( J . Amer. Chem. Xoc. 1921 43 1945-1950).-2 2'- XuZphonidotriphenylcarbi?zol HOCPh<C6H")S02 m. p. 224- 225" was obtained by the oxidation of phenylthioxanthenol or by the action of magnesium phenyl bromide on benzophenone sulphone. When heated with phosphorus pentachloride a t 110-120" i t yielded 2 2'-sulphonidotriphenylcarbinyl chloride m. p. 160-161" which when reduced with stannous chloride and hydrochloric acid gave 2 2'-sulphonidotriphenylmethune m.p. 193-194". The carbinyl chloride when shaken in benzene solution with molecular silver gave the free radicle 2 2'-sulphonidotriphenylmethyl m. p. 180" (decomp.) which when exposed in benzene solution to air yielded a crystalline peroxide m. p. 238-239" (decomp.). The oxygen and iodine absorptions of the free radicle were determined and molecular-weight determinations in benzene and in p-bromotoluene as solvents indicate little change in molecular weight with rise in temperature from 6" to 27". The free radicle in solut'ion is unimolecular to the extent of 30% to 38%. The Anhaloniwn Alkaloids. 11. Constitution of Pellotine Anhalonidine and Anhalamine. ERNST SPATH (Monatsh. 1921 42 97-1 15).-If pellotine actually possesses the constitution suggested (A.1919 i 548) protection of its phenolic hydroxyl C6H4 W. G.i. 164 ABSTRACTS OF CHEMICAL PAPERS. group by introduction of a carbethoxyl or an ethyl radicle and cautious oxidation of the resulting compound by means of per- manganate should yield substituted gallic acids. No trace of the latter could however be obtained and similar failure to detect trimethylgallic acid was experienced on oxidising a methylated anhalamine. The view that pellotine and anhalonidine are deriv- atives of mezcaline containing a phenolic hydroxyl group cannot be maintained as it is found that dimethylmezcaline methiodide is identical with neit,her methylpellotine methiodide nor dimethyl- anhalonidine methiodide. These results suggest that the nitrogen in the two bases forms part of a closed ring and this view is confirmed by the observation that when heated with alkali hydroxide the quaternary com- pletely methylated pellotine methiodide gives an amine which when again combined with methyl iodide and subsequently boiled with alkali hydroxide is converted into a nitrogen-free compound.On the assumptions that the ring in question is the isoquinoline ring that Heff ter’s formula CI3H1,O3N for pellotine is correct and that the base contains a phenolic hydroxyl group a methyl group united to nitrogen and a gallic acid residue various con- stitutions are suggested for pellotine methyl ether; the most probable of these is 6 7 8-trimethoxy-1 2-dimethyl-1 2 3 4- tetrahydroisoquinoline which best expresses the relationship of pellotine to mezcaline and explains the optical inactivity of pello- tine the formation of the latter from mezcaline being brought about by ring closure by means of acetaldehyde so that assumption of enzyme action is unnecessary.The methiodide of 6 7 8- trimethoxy-1 2-dimethyl-1 2 3 4-tetrahydroisoquinoline pre- pared synthetically from mezcaline is identical with methylpellotine methiodide and since pellotine contains a hydroxyl group in place of a methoxyl group of the synthetic base Heffter’s formula C,,H,,O,N for pellotine is confirmed. The identity of the methiodides of the completely methylated derivatives of pellotine and anhalonidine shows that these two bases have the same ring system. Further the formation of N-acyl derivatives of anhalonidine demonstrates the latter to be a secondary base so that O-methylanhalonidine OMe/(\/\ should have the annexed constitution (I) which (I INH accords with the observation that the N-m- nitrobenzoyl derivative of the synthetic base OMe Me (I) is identical with methyl-N-m-nitrobenzoyl- (1.1 anhalonidine ; the formula for anhalonidine is therefore C1,Hl,O3N and not as Heffter thought C,,H,,03N.Thus pellotine and anhalonidine are derivatives of 6 7 8-tri- met hoxy- 1 -meth yltetrahy droisoquinoline but which of the three methoxy-groups exists as hydroxyl in the original bases remains undecided. As regards anhalamine it appeared possible that this represents N-methylmezcaline with a hydroxyl in place of one of the methoxy- groups. The non-identity of the methiodides of dimethylmezcaline and dimethylanhalamine shows however that anhalamine is notORGANIC CHEMISTRY.i. 165 of the mezcaline type and the further observation that O-methyl- anhalamine fails to yield the trimethyl ether of gallic acid when oxi- dised proves that the nitrogen atom does not occur in an open side- chain and indicates that this compound may be OMe/\/\ an isoquinoline derivative of the structure (11). OMel INH The accuracy of the latter is proved by the facts \/\/ that this compound is readily synthesised from mezcaline and formaldehyde and that it gives an OMe (11. f N-m-nitrobenzoyl derivative identical with N-m- nitrobenzoyl-0-methylanhalamine ; further the quaternary iodides of the base (11) and 0-methylanhalamine are identical. Anhalamine is therefore the dimethyl-ether of 6 7 8-trihydroxytetrahydroiso- quinoline but here also the position of the non-methylated phenolic hydroxyl is unknown.Heffter's formula C,,H,,O,N for anhalamine is thus confirmed. Of the anhalonium alkaloids anhaline and mezcaline belong to the P-phenylethylamines occurring in various plant families and are almost certainly decomposition products of substituted phenyl- alanines resulting from the degradation of proteins. The presence in the same plants as anhaline and mezcaline of the tetrahydro- isoquinoline derivatives pellotine anhalonidine and anhalamine indicates that the latter are formed from the former by condensation with acetaldehyde or formaldehyde. 6 7 8-Trimethoxy-1-methyl-3 4-dihydroisoquinoline obtained by the action of phosphoric oxide on the N-acetyl derivative of synthetic mezcaline yields a picrate C1,H,,0,N,C,H,0,N3 m.p. 181-182" ; a platinichloride (C1,H1,03N),,H2PtC1 which forms orange crystals darkening at 199" m. p. 200-201" (frothing) and an aurichloride Cl,Hl,03N,HAuC1 which forms straw-yellow crystals m. p. 154-156". 6 7 8-Trimethoxy-1-methyl-1 2 3 4-tetrahydroisoquinoline formed from the preceding compound by catalytic hydrogenation in presence of platinum and palladium yields a picrate C,,H,,O,N,C,~,O,N m. p. 172-173" a platinichloride m. p. on slow heating 204-206" (decomp.) on rapid heating 210- 212"; and an aurichloride m. p. 147-148" (frothing). The action of methyl sulphate on this base gives 6 7 8-Trimethoxy-1 2-dimethyl-1 2 3 4-tetrahydroisoquino- line which is identical with methylpellotine and forms a picrate C1,H,,0,N,C,H30,N3 m.p. 167-168" an aurichloride m. p. 135- 136" and a platinichloride m. p. 216-217" (decomp.). Dimethylanhulamine methiodide C,,H,,O,NI forms crystals m. p. 211-5-212.5". 6 7 8-Trimethozy-1 2 3 4-tetrah1~droisoquinoline prepared from mezcaline and formaldehyde according to Decker and Becker's process (A. 1913 i 29l) forms a hydrochloride C,,H,,O,N,HCl m. p. 242-2243' an aurichloride m. p. 130-14Q0 (frothing) a platznichloride m. p. 207-208" cfrothing and blackening) and a picrate m. p. 184-185"; the quaternary iodide obtained by treating the hydrochloride with methyl sulphate and sodium (C1,H,,O,N >z H,PtC16 J VOL. cxxa i. gi. 166 ABSTRACTS OF CHEMICAL PAPERS.hydroxide and subsequently witch sodium iodide is identical with dime t hvlanhalamine met hiodide (vide s uwra 'I. N-m-"~itrobenzDylanhalamilze 'CI6Hl2b&( OMe) has m. p. 175-176" and its methyl ether Cl,H1lO,N,(OMe) m. p. 147-1 48". T. H. P. Conversion of Berberine into Palrnatine. EREST SPATH and NORBERT LANG (Ber. 1921 54 [B] 3064-3074).-Palmatine has been isolated from calumba root by OMe//\/\ Feist (A. 1908 i 101) and subsequently 0Mel 11 the annexed formula has been assigned to it by Feist and Sandstede (Arch. Pharm. II I 1918 256 I). The close similarity of this \N\OMe formula to that of berberine has induced I "OMe the authors to attempt to confirm it \/ by direct synthesis. For this purpose bromopapaveriiie was reduced by granulated tin and hydrochloric acid to tetrahydrobromopapaverine a.p. 11 1" (+xH,O) m. p. 71-73" which was treated with a mixture of glacial acetic acid hydrochloric acid water and methylal. A small amount of a product m. p. 151-153" was thus obtained which was possibly bromote+urahyclropalmat8ine. Debromination of this substance by hydrogen in the presence of palladised barium sulphate did not yield tetrahydropalmatine but norcoralydine (cf. Pictet and Tsau Quo Chou A. 1916 i 418). The possibility of removing the hydroxymethyleiie group of berberine and replacing it by two methoxyl groups (thus giving palmatine) has becn examined. Orientating experiments with piperonal and tctrahydroberberine showed that the hydroxy- methylene group can be removed with some difficulty by dilute hydrochloric acid under suitable conditions but simultaneously the phenol produced is very est8eiisively resinified by the liberated formaldehyde. Better results were obtained with tetrahydro- berberine and methyl alcoholic potassium hydroxide solution in an evacuated tube at 180"; it is remarkable that under suitably chosen conditions the hydroxyinethylenc group can be removed whereas the two methoxyl groups remain intact.Nuclear con- densation by the liberated formaldehyde appears to occur to only a slight extent probably owing to the rapid transformation of the aldehyde into potassium formate and methyl alcohol. Methylation of the product of the change by diazomethane gave a poor yield of tetrahydropalmatine. Better results were obtained by its complete methylation by treatment with a large excess of methyl sulphate and alkali in the absence of oxygen and isolation of the completely methylated quaternary iodide by addition of potassium iodide and potassium hydroxide.The salt was found to be identical with tetrahydropalmatine methiodide. When distilled in a vacuum it gave tetrahydropalmatine identical with the product derived from natural sources. It was oxidised by a solution cf iodine in \/\A alcohol to palmatine. IT. w.ORGANIC CHEMISTRY. i. 167 A New Bass from the Residues of the Hydrolytic Products of Cocaine Isomeric with Tropine and $-Tropine. J. TROGER and K. SCHWARZENBERG (Arch. Pharm. 1921 259 207-226).- By fractional crystallisation from alcohol of the hydrochlorides of the basic residues left after the removal of the ecgonine from the product of the hydrolysis of the coca alkaloids the hydrochloride of a new base isomeric with tropine and $-tropine was isolated from the more soluble fracbions.The new base C,HI5ON is a very hygroscopic crystalline substance m. p. 53" b. p. 225-230" and distinctly volatile a t the ordinary temperature. The hydro- chloride hydrobromide and hydriodide are crystalline salts very soluble in water and alcohol and melt at 157-160" 175" and 186" respectively. The picrate C,H,5QN,C,H,(M0,),*OH forms hygroscopic yellow needles which sinter a t 225" and decompose a t 237". The pZatinichZo&Ze ( C,H~50N),,H,PtCI is also very soluble in water and was obtained in long yellow needles m. p. 184" by evaporating the aqueous solution to dryness and crystal- lising from absolute alcohol and ether.The preparation of the aurichloride in an analytically pure state presented difliculties owing apparently to partial reduction and varying gold content of the salt. The benxoyl derivative crystallised from a mixture of alcohol and ether formed glistening white prisms m. p. 139-140". The inethiodide of the base crystallises from alcohol in well char- acterised white needles m. p. 238-240". It was converted into the corresponding ammonium base by means of silver oxide and this on distillation gave trimethylamine and a residue giving no solid derivatives and otherwise not further examined. Attempts to oxidise the original base with chromic acid permanganatc ferricyanide and hydrogen peroxide were either without result or gave oily products from which colid derivatives could only in one or two instances bc obtained and Ghen not in an analytically pure condition.G. F. M. Ecgonine. LXIX. J. G:SDAMER and G ~ I ~ L JOHN (drc7~ Pharm. 1921 259 227-240).-0f the two possible formulx! for anh ydroecgonine FH,- QH-FH*CO,H qH,- yH-S*CO,H (I.) I ?Me EH (11.) I __ YMe GH ? CH,-CH-CH CH,-C H-CH Willstatter decided in favour of I (A. 1899 i 178) but i t is now shown that formula I1 must be correct since on reduction to hydro- ecgonidine a t least two different optical isomerides are produced which could only be the case by the creation of a third asymmetric carbon atom and on the basis of formula I this is not possible without assuming the occurrence of isomerisation during the reduction.Such isomerisation is conceivable if the reduction is carried out by Willstatter's method with sodium and amyl alcohol but t'he hydrogenation was also carried out by the Paal and Skita method in which an isomerisation is extremely unlikely and two 9 2i. 168 ABSTRACTS 03' CH.EMICAL PAPERS. hydroecgonidines were again obtained. I n each case the optical isomerides were separated through their aurichlorides. For further confirmation the ethyl esters of the various aurichlorides were also prepared. Hydroecgonidine prepared by the reduction of the hydrogen bromide additive product of anhydroecgonine was an individual substance identical with one of the isomerides obtained by Paal and Skita's method. As according to formula 11 anhydro- ecgoiline contains a conjugated system of double bonds an exalta- tion of the molecular refraction was expected as compared with hydroecgonidine.Determination of the molecular refractions of the ethyl esters in each case showed this expected exaltation although anhydroecgonine ethyl ester considered by itself actually showed a depression which must be attributed however to the pyrrolidine ring. The following were prepared during the investi- gation Hydroecgonidine hydrochloride by Willstatter's method m. p. 233-234" [a]D-3*0° giving two aurichlorides m. p. 210" and 230" respectively which on reconversion into hydroecgonidine hydrochloride yielded two corresponding isomerides both melting a t 233-234" but having [a]= -2.77" and -4.4" respectively. Reduction by the Paal-Skita method gave a product which was also resolvable into two aurichlorides m.p. 210" and 220" respec- tively and these on reconversion gave two hydroecgonine hydro- chlorides having [ a]? -2.30" and - 1.24' respectively. The hydro- ecgonine hydrochloride prepared by the reduction of the hydrogen bromide additive product of anhydroecgonine with zinc and sul- phuric acid gave only one aurichloride m. p. 210" [.ID +2.7S0. The aurichloride m. p. 210° gave an ethyl ester melting at 173- 174" and the aurichloride m. p. 220" an ethyl ester m. p. 123". The ethyl ester obtained from the dextrorotatory aurichloride melted a t 173-174" and gave an ester hydrochloride having CaID +54. G. F. M. ERNST SPATH and NORBERT LANG (Ber. 1921 54 [B] 3074-307S).-The annexed formula has been assigned to corydaline by Dobbie oMe/\/\ and Lauder (P.1902 17 252) and after OMei II IN consideration of several alternative expres- sions has been adopted by Gadamer. I 1 The positions of the methyl group and of \ & ) M e the two methoxyl groups attached to the ( IlOMe benzene nucleus have not however,. been \/ placed beyond doubt and for this reason the authors have attempted the synthesis of a number of these compounds. If the above formula be correct corydaline is to be regarded as methyltetrahydropahatine (cf. Spath and Lang this vol. i 166). The latter substance however is found not to be identical with r-corydaline or mesocorydaline. Dobbie and Lauder's formula therefore appears to be inexact. Palmatine iodide is converted by magnesium methyl iodide in ethereal solution ink0 cc-methy~dihydropalmatine yellow needles m.p. 128-130" which is reduced by platinised zinc and dilute The Constitution of Corydaline. \/\/\MeORUANTC CHEMISTRY. i. 169 sulphuric acid to a mixture of a-m~,thyll~fsa7~ydi~o~~Zmat~nes greenish- ycllo~v lea'flet~s 111. p. 165" and m. p. G7-69" respcctively. H. W. Codeineoxidesulphonic Acids and their Derivatives. EDMUND SPEPER and HERMANN WIETERS ( B e y . 1921 54 [B] 253764987) .-The action of acetic anhydride and sulphuric acid on codeine-N-oxide has been shown by Freund and Speyer (A. 1911 i 809) to lcad t o the formation of a-codeine-Lv-oxidesul- phonic acid C,,H,,O&~BH)>O SO - and codeine-N-oxidesulphonic . . acid C18H2003<g(&H which are reduced by sulphurous acid to the same codeinesulphonic acid.The behaviour of the iso- meric sulphonic acids when catalytically hydrogenated is now clescri bed. Codeine-N-oxidesulphonic acid is reduced by hydrogen in the presence of colloidal palladium to dihydrocodeinesulphonic acid (annexed formula) six-sided leaflets or SO,H well-defined prisms decomp. 330-340" after darkening at 30" [a] -76.7" in faintly alkaline solution. The same acid is obtained by catalytic hydrogenation of codeinesulphonic acid. The acid is re- converted by water at 150" or by stannous chloride and concentrated hydrochloric It is acid a t 100" into dihydrocodeine. transformed by nitric acid (d 1.36) into nitrodihydrocodeine yellow double pyra- mids m. p. 221" identical with the sub- stance described by Freund and Melber (A.1920 i 717). Similarly x-codeineoxidesulphonic acid yields a-dihydrocodeinesulphonic acid a colourless crystalline powder decomp. 315-320" [a] - 88" in aqueous solution ; the corresponding monohydrate is also described. It is converted by water at 150-160" i n t e dihydrocodeine and by cold nitric acid (cl 1-36) into ~-nitrodi~~?ldrocodej~~ slcncler yellow needles in. p. 1130". At tempts werc also made to prepare the isonieric dihydrocodeine- siilphonic acid from di hydrocodeine. For this purpose the latter was trnnsforiiiccl by hydrogen peroxide into dii~ydrocodeine-N-oxid~ pale yellow rhombic crystals decomp. 226" after softening at 215" (hydyochloride hexagonal plates m. p. 217" after previous softening ; picrate four-sided prisms m. p. 161-162"). Under the action of siilphuric acid and acetic anhydride the latter yields a single dihydrocodeine-N-oxidesulphonic acid C,,H,,O,NS prisms decomp.273-275" which is reduced by sulphurous acid to dihydrocodeine- sulphonic acid. The applicability of sulphoacetic acid for the sulphonation of derivatives of codeine has been tested further in the case of chloro- dihydrocodide-N-oxide (cf. Freund and Melber loc. cit.). It has been found possible to isolate a chlorodihydrocodide-N-oxidesulphonici. 170 ABSTRACTS OF CHEMICAL PAPERS. SO,H acid (annexed formula) feathery crystals decomp. 290-295" but the occurrence of an isomeride could not be observed. The acid t! /I is reduced by sulphurous acid to chZorodi- /\/\ hydrocodidesulphonic acid prisms decomp. o\ CH CH Dihydrocodeinesulphonic acid after '\ /\/ \ ,Me neutralisation by sodium hydroxide is con- $? verted by an excess of methyl iodide into H>c '' -0% c H2 dihydrocodeinesulphonic acid methyzhydroxide \/ .I ../ C,,H,,O,NS rectangular plates decomp.c1 280-285"; the latter is very stable towards water but is decomposed by sodium hydr- oxide solution (4%) at 140" into tetramethylethylenediamine and a nit,rogen-free substance which could not be isolated. I n view of the mutability of the codeine molecule it is possible that the formation of isomeric sulphonic acids is due t o preliminary isomerisation of the codeine itself. I n this case it must be possible to derive one of the sulphoiiic acids from an isomeric codeine. I n this connexion $-codeine has been transformed by hydrogen peroxide into +-codeine-N-oxides prisms m.p. 226-228" (picrate needles m. p. 166-168") which is transformed by a mixture of acetic anhydride and sulphuric acid into $-codeine-N-oxidesdphonic acid long glassy prisms decomp. about 300" which is not identical with cx-codeineoxidesulphonic acid akhough resembling it in being soluble in water. H. W. O M e d \ / I yHz about 300". FH y'% CH CH2 1-a-N-Methylpiperidylethane-1-one. KURT HESS and PVz- HELM CORLEIS (Ber. 1921 54 [B] 3010-3020).-The synthesis of 1-cr-N-methylpiperidylethane-1-one is described the method adopted being similar to that used in the preparation of the corre- sponding propane derivative which the new substance resembles closely. Unexpectedly its transformation into hygrine could not be realised on account of the failure to effect demethylation to the secondary amine.a-Pyridyl methyl ketone is catalytically hydrogenated in the presence of platiiiuni to a mixture of the diastereoisomeric forms of 1-a-pi~eridyletlzane-1-oZ b. p. 106-110"/18 mm. which is converted by formaldehyde and formic acid into a mixture of 1-cr-N-methyl- 13i~eridyZethane-a-ols b. p. 94-106"/22 mni. The latter is oxidised by chromic acid in acetic acid solution t o 1 -cr-N-meth?lZ~iperidyZ- ethane-a-one C,NH,Mc*COMe a mobile hygroscopic liquid b. p. 78-80"/14 mm. which decomposes somewhat rapidly when pre- served. The picrate short prisms m. p. 119-EO" semicarbnxone m. p. 175-177" methiodide small plates m. p. 144" and a non- homogeneous hydraxone b. p. 115-117°/15 min. [picrate of latter m.p. 189" (decomp.)] are described. The hydrazone is converted by a solution of sodium ethoxide in alcohol at' 160-170" into 1-a-N-methylpiperidylethane (picrate m. p. 170-171"). The ketone does not react with ethyl azidodicarboxylate. It reactsORGANIC CHEMISTRY. i. 1'71 with cyanogen bromide to form the expected methobromidc (auri- chEoride of the corresponding methochloride C,H,,ONCl,AuCl ochre-yellow crystals m. p. 142") and cyanamide derivative but the hydrolysis of the latter leads to the product'ion of a non-basic substance (which was not obtained in the pure state but is probably an imidazolone derivative) in place of the desired secondary ketone. The action of formaldehyde and hydrochloric acid on 1 - cc-piper- idylethane-1-01 a t 120-130" leads ' '-yHMe (4 - - - r M e to the production of the oxazol- idine derivative (annexed formula I) b.p. 79-81"/18 mm. (picrate slender needles m. p. 163") whereas the corresponding oxnzol- idone (annexed formula 11) b. p. 164"/14 mm. is obtained when the urethane of 1 - ec-piperidylethane- a-ol is distilled under diminished pressure. H. W. /\ /\ \/ co / r;J / O CH (1.1 (11.) The Preparation of Pyridine and of certain of its Homo- logues in a State of Purity. JOSEPH GREENWOOD HEAP WILLIAM JACOB JONES and JOHN BAMBER SPEAKMAN ( J . Amer. Chem. Xoc. 1921 43 193&1940).-Pyridine 2-methylpyridine and 3-methylpyridine were separated from the crude coal tar bases from a light oil by repeated fractional distillation and subsequently purified through their additive compounds with zinc chloride. 2 6- and 2 4-Dimethylpyridines were similarly obtained from the crude bases of middle oil but purified through their mercuri- chlorides.The following physical constants using special pre- cautions were obtained pyridine b. p. 115.3" ; c71y 0.9776 ; 2-methylpyridine b. p. 128-129" ; @j 0.9404 ; 3-methylpyridine b. p. 143.8"; dt5 0.9515; 2 6-dimethylpyridine b. p. 137.5"; &ii 0.9200; 2 4-dimethylpyridine b. p. 157.1" ; dy 0.9273. w. G Some Physical Properties of Aqueous Solutions of certain Pyridine Bases. WILLIAM JACOB JONES and JOHN BAMBER SPEAK- MAN ( J . Amer. Chern. Xoc. 1921,43,1867-1570 ; compare preceding abstract) .-The densities of aqueous solutions of pyridine %methyl- pyridine and 3-methylpyridine have been determined a t 25".In the case of pyridine the density rises with increasing concentration of water to a maximum (1.0032) a t 50% water; in the other cases the density rises regularly with increasing concentration of water. The composition of the constant boiling mixture of each of the three bases is determined a t various pressures and it is shown that a t ordinary pressures the constant boiling mixture with pyridine contains 42% of water with 2-methylplyridine 48% of water and with 3-methylpyridine 61% of water. The boiling points of the mixtures are respectively 93.0" 93.5" and 96.2". The miscibility of 2 4-dimethylpyridine with water has been investigated. It is shown that the minimum critical solution t'emperature is 22.5",i. 172 ABSTRACTS OF CHEMICAL PAPERS.and the boiling point of the constant boiling mixturc is 966". The distillate condensed into two layers but on cooling below 23.2" it became homogeneoils and contaiiied G6y0 of water. J . F. 8. 5-Methox ydioxindole and 5 -Met hox yis at in. J . H ALB ER - KANN (Ber. 1921 54 [B] 3079-3090; cf. this vol. i 174).- The experiments described were undertaken in the hope of discovering a convenient method for the preparation of quinic acid in quantity ; they were not completely successful. Ethyl mesoxalate condenses with p-anisidine in hot glacial acetic acid solution to give ethyl 3 - hydroxy - 5-methoxy-2 - ketod:h ydroindole- 3 -carboxylate yH*76H3*0Me coarse colourless needles or plates C 0 *C( OH WO,E t' 3 m. p. 193-194'. The yiAd is 33-37% of that theoretically possible and is not improved by the addition of anhydrous sodium acetate or of acetic anhydride.A by-product brownish-yellow rectangular platelets or needles m. p. 256" is also formed. The ester is not produced when its components are melted together. It is converted by acetic anhydride and sodium acetate into the corresponding diacetyl compound colourless rhombohedra m. p. 122-123" and by a large excess of phenylhydrazine or hydroxyl- amine into 5-methoxyisatin-3-phenylhydrazone m. p. 216-217" (Bauer A. 1909 i 467 gives m. p. 219") and 5-methoxyisatin- 3-oxime brownish-red intertwined prismatic needles m. p. 234- 235". Hydrolysis of the ester with potassium hydroxide and subsequent acidification with hydrochloric acid leads to the separ- ation of 5-methoxydioxindole long colourless to pale brown four- sided needles m.p. 204-205" [diacetyl compound colourless rhombohedric prisms m. p. 225-226" (decomp.).] When an ice- cold solution of the dioxindole in alkali is acidified with acetic acid 2-amino-5-methoxymandelic acid colourless plates or rhombohedra (+lH,O) separates. It has m. p. 160-161" (evolution of steam) when heated rapidly after which it resolidifies and melts again at 203-204" (m. p. of 5-methoxydioxindole). An aqueous suspension of the acid is coloured brown green bluish-violet and ultimately dark red by ferric chloride; the action does not depend on complex salt formation since a similar effect is produced by bromine water. A diazotised solution of the acid couples with an alkaline solution of p-naphthol t o give a dark reddish-violet dye.The stability of the acid is remarkable since o-aminomandelic acid appears to lw incapable of existence. 5-Methoxydioxindole is only converted with difficulty by air or oxygen into 5-methoxyisatin; as a rule the action only procecds to the formation of the methoxylated isatyde m. p. 246" (decomp.) after softening at 135" ( ? water of crystallisation). 5-.Methoxyisatin almost black prismatic needles is however readily produced from the dioxindole by the action of very dilute ferric chloride solution. When boiled with an alcoholic solution of aniline 5-methoxyisatin yields the corresponding 3-aniZide lustrous orange-red needles m. p. 223" which dissolves to a dark green solution in concentratedORGANIC CHEMISTRY. i. 173 sulphuric acid.OM,{)/\ \/\/ NH The acetyl derivative of 5-methoxyisatin forms red prismatic needles or coarse prisms m. p. 144-145". When the isatin is /\ melted with o-phenylenediamine it >c-N-( I gives 10-methoxyindophenaxine (an- \/ nexed formula) m. p. 247" which sublimes in long orange-yellow C-.- N-l I needles when heated cautiously. H. W. Bromo-2-methylquinolines. K. L. MOUDGILL ( J . Arner. Chem SOC. 1921 43 2257-2258).-6-Bromo-2-methylquinoline is prepared by the condensation of p - bromoaniline and paracetaldehyde in hydrochloric acid (cf. Bastow and MacCollum A. 1904 i 686). It gives a methiodide m. p. 237" (decornp.) and an ethiodide m. p. 218". m-Bromoaniline condenses with paracetaldehyde to give (?)-bromo-2-methylpuinoline m. p. 77" giving an ethiodide m.p. 217"; a nitrate m. p. 102"; a xincichloride m. p. 268"; a stanni- chloride; a mercurichloride m. p. 245"; and a picrate m. p. 207". Whether the bromine atom is in position 5 or 7 has not been settled. W. G. Constitution of Kynurenic Acid. ERNST SPATH (Monatsh. 1921 42 89-95).-Kynurenic acid regarded by Camps (A. 1901 i 751) as 4-hydroxyquinoline-3-carboxylic acid was shown by Homer (.A. 1914 i 730) to have m. p. 289" which is that of the 4-hydroxyquinoline-2-carboxylic acid obtained by Camps. Neither Camps nor Homer however compared derivatives of natural kynurenic acid with those .of the synthetic hydroxyquinolinecarb- oxylic acid and Ellinger and Matsuoka's work (A. 1920 i 696) on the conversion of tryptophan into kynurenic acid in the animal body appears to indicate the accuracy of Camps's constitution for the acid.The author finds that kynurenic acid may be rapidly freed from protein compounds by conversion into its methyl ester the hydro- chloride of which is sparingly soluble in methyl alcohol. Treat- ment of the pure kynurenic acid with phosphorus pentachloride yields a 4-chloroquinolinecarboxylic acid and catalytic replacement of the chlorine by hydrogen in presence of palladium and barium sulphate yields quinoline-2-carboxylic acid which was identified by means of its methyl ester and amide. Further the methyl ester the methyl ester of the methyl ether and the benzoyl- methyl ester of synthetic 4-hydroxyquinoline-2-carboxylic acid agree in properties with the corresponding derivatives of natural liyiiurenic acid. The contradictory results of Camps and Homer appear to be clue to the fact that the melting point of kynurenic acid varies from 255" to 289" according to the rapidity of the hcatiiig.Methyl Icynure r Lute rtzeth yl ether (methyl 4 - methoxyquinoline-2 -curb - ox&&) C,,H,,O,N has m. p. 148-140" and methyl benxoyl- I;yiture?utc C,,H,,O,N forms whitc crystals 111. p. 143". T. H. P. 0"i. 174 ABSTRACTS OF CHEMICAL PAPERS. Derivatives of Qwinic Acid. J. HALBERKANN (Ber. 1921 54 [B] 3090-3107).-A record of the preparation of derivatives of quinic acid from 5-methoxyisatin (cf. Halberkann this vol. i 172). 5-Methoxyisatin condenses with pyruvic acid in alkaline solution to form 6-methoxyquinoline-2 4-dicarboxylic acid almost colourless prismatic rods or prisms m. p.239-240" (evolution of carbon dioxide). The lead copper silver and ferric salts were prepared. When heated with concentrated hydrochloric acid under pressure the acid is converted into 6-hydroxyquinoline-2 4-dicarboxylic acid small needles or plates (+lH,O) m. p. 318" which couples with diazoniuin salts in the usual manner. [The ammonium hydrogen salt needles (+lH,O) has m. p. 318" (decornp.) after becoming discoloured a t 285O.I 5-Methoxyquinoline-2 4-dicarboxylic acid loses carbon dioxide when heated slightly above its melting point and passes into 6-methoxyquinoline-4-carboxylic acid (quinic acid) which is identical with the substance derived from quinine. The direct production of quinic acid from 5-methoxyisatin and acet- aldehyde is impossible since the latter becomes resinified by the alkali whilst if acetoxime is used it is difficult to remove the methoxy- p-isatosime formed simultaneously.Attempts to prepare the acid directly from p-anisidine (cf. Pictet and Mesner A 1912 i 650) by replacing the pyruvic ester by the free acid and methylal by ethyl orthoformate gave only small yields of the desired substance. 6-Methoxyquinoline-2 3 4-tricarboxylic acid aggregates of needles (+ lH,O) m. p. 224-225" (decornp.) after previous darken- ing is prepared by the condensation of 5-methoxyisatin and ethyl oxalacetate in concentrated alkaline solution. 5-Methoxyisatin and acetophenone in hot alcoholic alkaline solution give 6-methoxy- 2-phenylquinoline-4-carboxylic acid pale yellow needles (+ lH,O) m.p. 236" which howevcr is prepared more conveniently from p-anisidine benzaldehyde and pyruvic acid. When triturated with hydrochloric acid (d 1*125) the acid gives an intensely yellow lzydrochloride which is decomposed readily by water. When heated with concentrated hydrochloric acid under pressure the methoxy- acid is converted into 6-hydroxy-2-phenylquinoZine-4-carboxylic acid yellow needles m. p. 330" (decomp.). The latter couples with diazotised sulphanilic acid giving 5-p-sulphobenxenaxo-6-hydroxy- 2-phe~zylquinoline-4-cnrbozylic acid a red structureless powder which darkens above 200" and gradually becomes carbonised without melting a t a higher temperature. The corresponding aniline salt dark red prisms behaves similarly when heated. The azo-dye is reduced by sodium hyposulphite to 5-amino-6-hydroxy- 2-~7tenylquinoEine-4-cnrboxylic acid an unstable substance which passes readily into the corresponding quinone.6-Methosy-2-phenylquinoline-4-carboxylic acid is smoothly con- verted by the calculated quantity of potassium nitrate in the presence of concentrated sulphuric acid into 6-nitro-6-methoxy-2- p hen y lquinoline- 4-carbox y lic ac id long pale- yello w rectangular platelets m. p. 262" (decornp.) when rapidly heated after darkeningORGANIC CHERIISTRY. i. 175 above 250". It is reduced by ferrous hydroxide in alkaline solution to 5-amino-6-met7~oxy-2-phenyl~uinoline-4-carboxylic acid rosettes of violet-red needles or platelets m. p. 255-256" (decomp.). After being diazotised it couples with p-naphthol in alkaline solution to yield 5-h ydroxynuphthuleneaxo- 6-methoxy-2 -phenylqzcinoline-4 -curb - oxylic acid almosb black granular aggregates which do not melt below 300".When the amino-compound reacts in sodium car- bonate solution with diazotised sulphanilic acid it yields 8-p-~~lpho- benxeneaxo-5-hydrozy-6-methox~-~-p~~e~aylqu~noline-4-carboxyl~~ acid a violet powder m. p. 205" (decomp.) after softening a t 190". According to the author's unpublished observations a similar replacement of the amino- by the hydroxy-group during coupling is shown by 5-aminohydroquinine. Deoxybenzoin and 5-methoxyisatin give 6-methoxy-2 3-diphenyl- quinoline-4-carboxylic acid colourless needles m. p. 306" (decomp.). With acetone 5 -methoxyisatin yields 6 -methoxy -2 -meth ylquinoline - 4-carboxylic acid bluish-yellow needles m.p. 286" which is obtained more conveniently from p-anisidine pyruvic acid and acetaldehyde. It is converted by concentrated hydrochloric acid a t 145" into 6- hydroxy-2 -methylquinoline-4-carbox ylic acid slender needles which begins to decompose above 300" with evolution of a brownish- yellow oil ( ? 6-hydroxy-2-methylquinoline) but is not completely melted a t 340". The methoxy-acid is converted by chloral into 6-mcthoxy-2 yyy-trichloro- A~-~ropenyEyuinoEine-4-carbox~l~~ acid colourless prismatic rods m. p. 216" (decomp.) after darkening above 190" which is transformed by alkali into 4-cccrboxy-6-methoxy- quinoline-2-P-acryEic acid OMe*C,H,< C(CO,H)*YH yellow slender needles m. p. 249" (decomp.) after darkening at about 220".The latter is oxidised by potassium permanganate to 6-methoxyquinoline-2 4-dicarboxylic acid. 6-Methoxy-2- (2') - furylquinoliize-.l-carboxylic acid prepared from 2-acetylfuran and 5-methoxyisatin or from p-anisidine furfur- aldehyde and pyruvic acid crystallises in yellow needles m. p. 241" (decomp.) after previous darkening. 1-Acetyl-5-methoxyisatin is quantitatively transformed (apart from the regenerated isatin) when heated with aqueous sodium hydroxide solution into 6-naethoxy-2- keto- 1 2-dihydroquinoEine-4- carboxylic acid dark yellow prismatic rods m. p. 326" (decomp.). When precipitated from its alkaline solution by mineral acids it forms an almost colourless gel ( ? 2-hydroxy-6-methoxyquinoline-4- carboxylic acid) which subsequently passes into the yellow variety.The latter does not couple with diazotised sulphanilic acid in sodium carbonate solution. Boiling glacial acetic acid converts that portion of it which remains undissolved into intensely yellow woolly needles m. p. 326" (decomp.). The corresponding ethyl ester small orange-yellow needles m. p. 231" after softening a t 205" can be obtained directly in small amount from p-anisidine and ethyl oxalacetate in glacial acetic but not in alcoholic solution. N-C*CH:CH*CO,H' H. W. g* 2i. 176 ABSTRACTS OF CHEMICAL PAPERS. Influence oE Substitution in the Components on Equilibria in Binary Solutions. XXXIII. The Binary Systems of Carbazole or Acenaphthene with Polynitro-derivatives of Benzene and Toluene. ROBERT KXEMANN and HUBERT STRZELBA (Monatsh.1921 42 167-180; cf. this vol. i 159).- The results obtained by Kremann and Slovak (A. 1920 i 564) show that the ability of picric acid to combine with carbazole depends on its nitro-groups the hydroxyls being inert. The authors find that no compound is formed in the solid state by carbazole with any one of the three dinitrobenzenes or with 2 4-dinitrotoluene simple eutectics being obtained in all cases. For 0- m- and p-dinitrobenzenes and 2 4-dinitrotoluene these eutectics correspond respectively with 107" and 15%; 72" and 13%;. 143" and 34% and 62" and 11% of carbazole. With s-trinitrobenzene (1 rnol.) carbazole (1 11101.) forms a compound which melts homogeneously (m. p. 203") with little dissociation and gives a eutectic with carbazole at 195" containing 44% of trinitrobenzene and a eutectic with trinitrobenzene a t 120" con- taining about 97.5% of trinitrobenzene.With 2 4 6-trinitro- toluene carbazole also forms a compound (1 mol. 1 mol.) which however exhibits considerable dissociation in the fused condition so that introduction of the electropositive methyl group appears to weaken the activity of the nitro-groups. Towards nitro-derivatives of benzene acenaphthene behaves similarly to naphthalene (Kremann and Haas A. 1919 ii 457). With 1 3 5-trinitrobenzene acenaphthene forms a compound (1 mol. 1 mol.) m. p. 161" which with acenaphthene gives a eutcctic corresponding with 87" and S% and with 1 3 5-trinitro- benzene a eutectic corresponding with 115" and 94% of the trinitro- benzene. With 2 4 6-trinitrotoluene acenaphthene forms a compound (1 mol.1 mol.) m. p. 112" (compare Buguet R. 1910 i l05) which gives a eutectic with acenaphthene a t 81" containing ISYO and it eutectic with trinitrotoluene at 72" containing 92% of trinitrotoluene. T. H. P. Triarylisooxazoles. JAICOB R~EISENHEIMER and KARL WEIBEZAHN (Ber. 1921 54 [B] 3195-3206).-By the action of potassium hydroxide solution on p -nitro - a-methox y - o! p -dip henyl- ethane or on 7-nitrostilbene and as by-product of the condensation of phenylnitromethane with benzaldehyde according to the method of Knoevenagel and Walter (A. 1905 i 65) Heim (A 1911 i 717) has isolated a substance which is regarded as 3 4 5-triphengl- . . . - I " The proof of the correctness of this HCPh.9 isooxazole CPh< CPh:N' formula is now givcn by the observation that the substance is oxidised by ozone to benzoylbenziloxime CPh(:N*QBz)Bz ; it is remarkable however that the benzoyl derivative of benzil p-oximo is produced in place of the expected a-compound (cf.Meisenheimer this vol. i 152). The constitution is confirmed further by synthesis of the compound from dibenzoylphenylmethane or tri- benzoylphenylmethane and hydroxylamine. Heim (Zoc. c k ) hasORGANIC CHEMISTRY. i. 177 advanced the theory that 3 4 5-triphenylisooxazole is formed from 7-nitrostilbene according to the scheme CHPh:CPh-NO -+ Ph-CHO + CH,Ph*N02 CHPh:CPh*NO + CH,Ph*NO addinon.+ NO,*CHPh*CHPh*CHPh*NO yo% CPh< In conformity -HNO CPh:N' with this conception it is shown that the yields of 3 4 5-triphenyl- isooxazole are increased very considerably when an equivalent amount of phenylnitromethane is added to the a-nitrostilbene before it is heated with potassium hydroxide.Further it is found that a-nitro-4'-methoxystilbene is convertible in good yield into 3 5-diphenyl-4-anisylisooxazole which can only be explained if it is assumed that the nitromethoxystilbene suffers partial fission to anisaldehyde and phenylnitromethane followed by condensation of the latter with unchanged nitromethoxystilbene. Several other substituted isooxazoles have been synthesised in a similar manner. Reaction proceeds smoothly if all three substituents or the two in the 3 and 5 positions are similar. If however the two latter are dissimilar two structural isomerides are generally produced simul- taneously.In the latter case a further complication ensues owing to the fact that the nitrostilbene suffers fission to the aldehyde and arylnitromethane the latter not being identical with the arylnitro- methane employed. This also condenses with unchanged nitro- stilbene and a complex mixture thus results from which it is impossible to isolate the desired isooxazole. F 3 4 5-Triphenylisooxazole slender colourless needles m. p. 212-213" is stable towards boiling alkaline permanganate and does not absorb bromine. It is converted by boiling nitric acid (d 1.4) into tri-p-nitrotriphenylisooxaxole m. p. 298-300" ; the simultaneous production of p-nitrobenzoic acid shows that the nitro-groups have entered into the p-position in the isooxazole compound.a-Nitro-4'-methoxystilbene is converted by boiling sodium hydroxide solution (15%) into 3 5-diphen?/Z-4-anisyZis~- oxaxole colourless slender needles m. p. 188-189". p-Methoxyphenylacetonitrile b. p. 152"/16 mm. is obtained in almost quantibative yield by the action of methyl sulphate and sodium hydroxide on p-hydroxyphenylacetonitrile and is converted by ethyl nitrate and potassium ethoxide according to the method of Wislicenus and Endres (A. 1903 i 472) into the potassium salt of p-anisyZisonitroacetonitriZe OMe*C,H,*C( :NO.OK).CN (the sodium salt was analysed) which is transformed by boiling sodium hydroxide solution into p-anisylnitromethane OMe*C,H,*CH,*NO b. p. 158-160"/11 mm. (the corresponding enolic form m. p. 65- 70° is unstable). p-Anisylnitromethane condenses with benzalde- hyde in the presence of a little methylamine to give a-nitro-4- methoxystilbene CHPh:C(NO,)*C,H,*OMe pale yellow crystals m.p. 95" and with anisaldehyde to yield a-nitro-4 4'-dimethoxy- stiZbene pale yellow crystals m. p. 140-141' b. p. 240-245"/16 mm. a-Nitro -4-methoxystilbene and p -anisylnitromethane yield 4-phenyl-3 5-di-p-anisylisooxaxoZe colourless needles m. p. 170- 172'. 3 4 5-Tri-p-anisyZisooxaxole small colourless needles,i . I78 ABSTRACTS OF CHEMICAL PAPERS. m. p. 146-147" is obtained from a-nitro-4 4'-dimethoxystilbene and p-anisylnitromethane. Phenylnitromethane and a-nitro-4 4'- dimethoxystilbene give 3( ? 5)-phenyZ-4 5( ? 3 4)-di-p-anisyZiso- oxaxobe colourless needles m. p. 156-157". a-Nitrostilbene and a-nitro-4'-methoxystilbene yield with p-anisylnitromethane mixtures of isooxazoles from which only the most sparingly soluble com- ponents namely triphenylisooxazole and 3 5-dipheny1-4-p-anisyl- isooxazole can be isolated in an approximately homogeneous condition.An ethereal solution of the sodium compound of deoxybenzoin (prepared by means of sodamide) is converted by benzoyl chloride mainly into tribenxoyZphenyZmethune colourless crystals m. p. 152". The course of the action is explained by the assumption of the initial formation of dibenzoylphenylmethane which as a relatively strong acid displaces the deoxybenzoin from its metallic derivative and forms the sodium compound of the diketone which reacts with a further portion of benzoyl chloride giving tribenzoylphenyl- methane.The latter is converted by hydroxylamine hydrochloride in glacial acetic acid solution in the presence of a little concentrated hydrochloric acid a t 200" into 3 4 5-triphenylisooxazole. If the alcoholic solution of the triketone is treated with sodium ethoxide or sodium hydroxide solution a t the atmospheric temperature it passes into dibenxoyZphenyZmethane lustrous pale yellow needles m. p. (indefinite) 148-151" after previous softening ; the latter can also be prepared under certain conditions from sodiodeoxy- benzoin and benzoyl chloride. When boiled for a considerable time with a quantity of alcohol insufficient for solution it is trans- formed into tribenzoylplienylmethane. It does not appear to be identical with the substance described by Japp and Lander (T 1896 69 742).H. W. Preparation of Anthraquinone Derivatives [l 2-Anthra- quinonylisooxazoles] . FARBWERKE VORM. MEISTER LUCIUS & BRUNING (Brit. Pat. 147001; 160433).-By the action of fuming sulphuric acid on 1-nitro-2-alkyl-anthraquinones or their sub- stitution derivatives products insoluble in alkalis and of great reactive power are formed which constitute valuable intermediates for the manufacture of anthraquinone dyes. The substances are produced by the elimination of 1 mol. of water from the nitro- alkylanthraquinone and they are probably isooxazole derivatives of the constitution C6H,<CO>C6H2<Ll >o 4 ap-Anthraquinonyl- isooxaxole prepared by mixing 1 part of 1 -nitro-2-methylanthra quinone and 20 parts of sand into a paste with 60y0 fuming sulphuric acid and pouring on to ice crystallises from xylene as a brownish- yellow powder sparingly soluble in the usual organic solvents and melting a t 250" (decomp.).7-Nitro-cc~-anthraquinonyZisooxaxole prepared by introducing 1 part of 1 5-dinitro-2-methylanthra- quinone into 15 parts of 40% fuming sulphuric acid with cooling and pouring the mixture on to ice crystallises from chlorobenzene as a greenish-yellow crystalline powder which decomposes without co Y C-RORCIANIC CHEMISTRY. i. 170 previous melting. 3-Methyl-a~-anthraquinonylisooxazole prepared in a similar way forms coarse dark brown crystals m. p. 210". 6 6 7 8-Tetrachloro-2-methylanthraquinone prepared in the usual manner from o-benzoyltetrachloro-p-methylbenzoic acid forms a pale greenish-yellow powder m.p. 192". On nitration it yields 5 6 7 8-tetrachloro- 1-nitro-2-methylanthraquinone pale yellow crystals m. p. 262" (decomp.). On treatment with fuming sulphuric acid at 5-10" the nitro-compound is converted into 7 8 9 10-tetrachloro-up-anthraquinonylisooxaxole forming yellow crystalline needles m. p. 242" (decomp.). According to the second patent (160433) the anthraquinonyl- isooxazoles are obtained in much greater purity if the reaction is conducted with exclusion of air for example in an atmosphere of carbon dioxide. G. P. M. NN'-Di(pallyloxypheny1)acetamidine. J. SCHULER (U.S. Pat. 1384637). NN'-Di(p-allyloxyphenyl)acetamidine colourless crystals m. p. 85-86' readily soluble in alcohol and ether and insoluble in water forming a hydrochloride m.p. 152-153" which dissolves easily in alcohol is less soluble in water and insoluble in ether is adapted for use as a local anzesthetic in ophthalmological practice. It is prepared by condensing allyloxyaniline with p - allyloxyacetanilide in the presence of phosphorus pentoxide or similar condensing agent. CHEMICAL ABSTRACTS. Action of Iodine on NW-Dialkyltetrahydro-4 4'-dipyridyls. BRUNO EMMERT and PAUL PARR (Ber. 1921 54 [B] 3168-3176; cf. A. 1909 i 602; 1917 i 221 ; 1919 i 455; 1920 i 331).- The action of iodine on the blue solutions of dimethyl- diethyl- and dibenzyl-tetrahydrodipyridyls has been shown to lead to the production of the corresponding alkylpyridinium iodides and of amorphous yellow substances containing iodine which have not been investigated more closely.The corresponding diisobutyl and diisoamyl compounds are now shown to react in a similar manner but in addition to give small nmount,s of the 4 4'-di- pyridyldialkyliodides R;>N<cH:cH>C*C<cH:cH ~ H T H CHoCH>N<R I ' * the mode of removal of the two hydrogen atoms in position " 4 " has not been elucidated fully. Diisoamyltetrahydrodip-yridyl is converted by iodine in alcoholic solution into a yellow amorphous product isoamylpyridinium iodide (platinichloride C20H,2N,C1,Pt pale yellow rhombic leaflets) and 4 4'-dipyridyl diisoamyliodirle ; the latter substance is obtained readily from its components. It crystallises in long thin red prisms m. p. 270-280" (decomp.). When the cold aqueous solution of the salt is agitated with silver oxide it gives a colourless solution of the base which becomes blue when warmed but again colourless when cooled or treated with air.The corre- sponding bromide green plates colourless chloride and plati92i- chloride long orange-yellow needles m. p. 260-270" (decomp.) are described.i. 180 ABSTRAUTS OF UHEMICAL PAPERS. 4 4'-Dipgridyl diisobutiodide red rhombic leaflets is prepared by the same methods as the isoamyl compound; the corresponding pZatinichZoride has m. p. above 300" (decomp.). The communication includes an exhaustive reply to the recent criticism of Weitz and Nelken (A. 1921 i 804). H. W. A Comparison of Three Isomeric Carbocyanines. WALTER THEODORE KARL BRAUNHOLTZ (T. 1922 121 169-173). spiroPyrimidines . 111.Condensation of cycZoPropane- 1 l-dicarboxylic Ester with Carbamides. ARTHUR W. Dox and LESTER YODER (J. Amer. Chem. Xoc. 1921 43 2097-2101; cf. A. 1921 i 360 740).-The yield of ethyl cydopropane-1 1- dicarboxylate from ethylene bromide and ethyl malonate by the action of sodium ethoxide (cf. Perkin T. 1885 47 808; 1887 51 849) was increased by modifying the conditions. The ester has b. p. 214-216"/748 mm. (corn.) the monoamide m. p. 195" and the diamide m. p. 198". The ester condensed with carbamide guanidine and thiocarb- amide to give stable amorphous compounds which were apparently not spiropyrimidines but polymerides. Hydrolysis of the poly- meride from carbamide followed by elimination of carbon dioxide gave a crystalline acid C,H,,O m. p. 152". The probable course of the condensation of the ester and carbamide is that cyclo- propane-1 5-spirobarbituric acid is first formed and this under- goes rearrangement to vinylbarbituric acid which tlhen polymerises giving a cyclobutanedibarbituric acid.The latter acid on hydrolysis and loss of carbon dioxide should yield cyclobutane-1 2- or 1 3- diacetic acid which could exist in cis and trans forms but such acids are not yet known. The Halogenated Indigotins. E. GRANDMOUGIN (Compt. rend. 1921 173 1363-1365).-1t is not possible to foretell with certainty the shade of colour of new indigotin derivatives. The marked influence of the positions 6 and 6' which prevent the tendency towards green of neighbouring groups as shown in the case of octabromoindigotin (cf. this vol.i 55) is further verified in the chloro-series where octachloroindigotin is more violet than the 5 7 5' 7'-tetrachloro-derivative. The absorption rays of certain di- and tetra-halogenated indigotins in solution in xylene or methyl benzoate are given. Constitution of the Dipeptides of Aspartic Acid. C. RAVENNA (Gaxxetta 1921 51 ii 281-284).-Both the dipeptide of aspartic acid obtained by Fischer and Koenigs from diketopiper- azinediacetic anhydride (A. 1907 i 486) and that prepared by Ravenna and Bosinelli (A. 1920 i 150 151) from asparagine yield voluminous precipitates with lead acetate but in the former case the precipitate is sparingly and in the latter case readily soluble in excess of the reagent. Further the former dipeptide gives only a distinct blue coloration with copper sulphate and potassium hydroxide whereas the latter gives the characteristic biuret reaction.Diketopiperazinediacetic anhydride has been prepared from W. G. W. G.ORGANIC CHEMISTRY. i. 181 each of the two dipeptides and from ammonium hydrogen malate; the t,hree preparations yield the p-dipeptide unmixed with u-isomeride when treated with barium hydroxide solution. It is possible also that the a-dipeptide may be obtainable directly from a-asparagine by boiling its aqueous solution. These results confirm the constitutions previously ascribed to the two dipeptides (A. 1920 i 600). 6-Amino-2-p-tolyl-u p-naphthatriazole. GILBERT T. MORGAN and SYDNEY CHAZAN (J. Soc. Chem. Ind. 1922 41 lT).-The investigation was undertaken with the object of securing a series of substituted a-naphthylamines capable of acting as middle components in the production of poly-azo-dyes.The difficulty with which they react with diazonium compounds however renders the 6-amino-2-aryl-ap-naphthatriazoles unsuitable for this purpose. On the other hand these aminotriazoles yield stable sparingly soluble diazo-derivatives which couple readily to form azo-compounds with the phenols and the more reactive aromatic bases. 5-Nitro-p-naphthylamine m. p. 140-142" is prepared by the action of concentrated sulphuric acid below -5" on p-naphthyl- amine nitrate and is converted by a diazotised solution of p-toluidine into p-toluene-l-axo-5-nitro-~-mphthylamine red; nodular crystals m. p. 197-199" after softening at 190". The latter substance is oxidised by chromic acid in acetic acid solution to 6-nitro-2-p-tolyl- c@-naphthtriuxole (annexed formula) yel- low flaky crystals m.p. 207-208". /\,<>*CG~&~ 6-Amino-2-p-tolyZ-u~-naphthtriazole has m. p. 178-180" ; the corresponding hydro- chloride m. p. 263-267" (decomp.) after I l l softening a t 240" and acetyl derivative \/\/ light brown needles m. p. 305-307" are NO2 described. A diazotised solution of the aminotriazole couples with p -naphth ol in alkaline solution giving p-tolyl- a p-na~hthtriaxoleaxo- p - naphthol m . p. (indefinite) 2 60-260 * . With p - nitro benzenediazo - nium chloride the aminotriazole gives 7-p-nitrobenxeneaxo-6-amino- 2-p-toZyl-ap-naphthtri~xole a sparingly soluble brownish-red com- pound m. p. 195-197" (decomp.) which is oxidised by chromium trioxide in hot glacial acetic acid to a brown bistriazole derivative m.p. 220-240" (decomp.) after softening a t 210". The Velocity of Reaction of Diazotisation in its Bearing on the Problem of Substitution in the Benzene Ring. 11. The Character of the Diazonium Group. H. A. J. SCHOUTISSEN (Rec. trav. chim. 1921 40 763-774; cf. Martinsen A. 1907 ii? 609).-As a result of failure in attempts to nitrate benzene- diazonium sulphate i t is inferred that the diazonium group is very strongly negative more so than the nitro-group and its directing influence on entering groups is towards the meta-position. Para- substituted-amino-diazonium compounds have also been dealt with and similar results obtained except in the case of the p-amino- phenoldiazonium compound.The author puts forward an T. H. P. H. W.i. 182 ABSTRACTS OF CHEMICAL PAPERS. alternative explanation t o that of Cain (T. 1907 91 1049) with regard to certain phenomena in diazo-compounds. Method for the Separation of Amino-acids from the Products of Hydrolysis of Proteins and Other Sources. HAROLD W. BUSTON and SAMUEL BARNETT SCHRYVER (Biochem. J. 1921 15 636-642).-A preliminary indication of a method whereby dicarboxylic amino-acids are precipitated by alcohol as barium salts after saturating their aqueous solution with baryta. If then without removing the alcohol carbon dioxide is passed into the solution other amino-acids are precipitated as barium carbamates (cf. Siegfried A. 1906 i 324). No individual amino- acid was isolated.G. B. Estimation of the Monoamiiio-acids in the Hydrolytic Cleavage Products of Eactalbwnin. D. BREESE JONES and CARL 0. JOHNS ( J . Biol. Chem. l921,48,347-360).-The following results were obtained Glycine 0.37% alanine 2.41 yo valine 3.30y0 leucine l443% proline 3.76% phenylalanine 1-25% aspartic acid 9.30% glutamip acid 12-89 yo hydroxyglutamic acid 10.OO~o serine 1*76y0 tyrosine 1.95y0. Swelling of Fibrin by Acids. R. SOMOGYI (Biochem. Z. 1921 120 103-105).-The swelling of fibrin by acids resembles the effect of acids on gelatin the acids following the same order of activity. The biologically important acids hydrochloric lactic and formic produce pronounced swelling. MARY A. GRIGGS ( J . Ind. Eng. Chem. 1921,13 1027-1028).-The maximum yield of amino- nitrogen (60% of the total nitrogen) is obtained when casein is heated at 150" under pressure for five hours with 10% sodium The Influence of Electrolytes on the Solution and Pre- cipitation of Casein and Gelatin.JACQUES LOEB and ROBERT B. LOEB ( J . Gen. Physiol. 1921 4 187-211).-Two types of colloidal solution exist. The first type is easily precipitated by small quantities of neutral salts the second requires much larger quantities. In the first type the particles go into solution as the result of swelling in consequence of the Donnan eqnilibrium and remain in solution as a result of the osmotic and electrical forces which the Donnan equilibrium necessitates. The second type is of the nature of true solution and there exist primarily only ions and molecules although aggregates may be formed secondarily.Measurements o€ the rate of solution of casein chloride in varying concentrations of acids and neutral salts indicate that the process of solution is regulated by the Donnan equilibrium and that it is of the first type. Here the effect of small quantities of neutral salts as precipitants is to reduce the osmotic forces and also the electric charges according to the theory of the Donnan equilibrium. Casein dissolves in sodium hydroxide solutions essentially like a crystalline substance and the solution is of the second type. Solutions of gelatin are also of this type although aggregates of H. J. E. E. S. H. K. Alkaline Hydrolysis of Casein. hydroxide solution. w. P. s.ORGANIC CREMTYTRY. i. 183 the dissolved particles tend to form on keeping (cf. A.1921 i 822). Experiments on the solubility and viscosity of gelatin solutions as influenced by neutral salts give evidence of the existence of these aggregates. W. 0. K. Swelling of Gelatin in Aqueous Solutions of Organic Acids. ALFRED KUHN (Koll. Chem. Beihefte 1921 14 147-208).-The swelling of gelatin in aqueous solutions of various concentrations of a large number of organic acids has been determined by the so-called volume method a t Z O O and from the results the increase in the swelling is ascertained in each case. A few experiments are described at O" 16" and 22" which were made to ascertain the influence of temperature on the swelling. The following acids were investigated Formic acetic propionic n-butyric isobutyric n-Valerie isovaleric isooctoic glycollic lactic chloroacetic dichloroacetic trichloroacetic bromoacetic cyanoacetic oxalic malonic succinic malic d-tartaric citric maleic fumaric amino- acetic henzoic m- toluic phenylacetic salicylic m- hydroxybenzoic mandelic benzenesulphonic sulphanilic cinnamic p ht halic pro to- catechuic gallic tannic and picric also hydrochloric sulphuric and nitric acids phenol quinol resorcinol catechol and naph- thalene-1-sulphonic acid.It is shown that with the exception of the sparingly soluble acids all acids show a swelling maximum a t a medium concentration. Swelling is the result of four simul- taneous processes of which a t least two operate in opposite directions. The first process is the actual swelling A (hydration) and is the chief process at low concentrations; opposed to this are sol formation and hydrolysis B ; the fourth process is dehydra- tion and coagulation.The swelling maximum is defined as that point at which the amount of swelling ( A ) with increasing con- centration is exceeded by the sol formation (peptisation) and the decreasing hydrolysis (23). No relationship between the maximum swelling and the degree of dissociation of the acids could be found but an approximate connexion between the concentrations a t which the maximum occurs and the strength of the acid was found. With strong acids the maximum swelling concentrations lie a t lower concentrations and with weaker acids a t higher con- centrations whilst with acids of medium strength the curve only shows a bend. The swelling maximum as the resultant of the hydration sol formation and hydrolysis shows no linear relation- ship rather especially in the case of acids of medium strength does the sol formation appear to play the greater r6le.The actual swelling in the region of small concentrations is well repre- sented by the equation h=pC'" in which h is the swelling height C the concentration of the acid and q and n are constants. The principal part of the swelling can be quantitatively represented by the constants q and n. Neither q nor n has any connexion with the strength of the acid and further the swelling maximum is not determined by either q or n. Hence it is shown that acids operate in the swelling of gelatin in the sense that a t lower con- centrations a specific increase in the power of binding water isi.184 ABSTRACTS OX CHEMICAL PAPERS. brought about. Whether thereby a chemical or adsorption com- pound is formed has not been settled. At higher concentrations sol formation and hydrolysis commence and at the same time dehydration and precipitation which are opposed to the actual swelling process. J. F. S. A New Function of the Tryptic Ferment (Anhydrase) and the Preparation of d-Tyrosine-anhydride and d-Tryptophan- anhydride from the Products of Tryptic Digestion. SIGMUND FRANKEL and EMIL FELDSBERG (Bi,ochem. Z. 1921 120 218- 229) .-Casein when digested with trypsin until the bromine test for tryptophan is negative yields a dextrorotatory tyrosine-an- hydride and a dextrorotatory tryptophan-anhydride. The amino- groups are free but the carboxyl groups are combined as in acetic anhydride. d-Tyrosine-anhydride has m.p. 273" and [ a],+37*59" in alkaline solution [ a],+93.87" in acid solution. d-Tryptophn- anhydride decomposes a t 230-245" and has [a],+20-59* in water. H. K. The Activity of Adsorbed Invertase. J. M. NELSON and DAVID I. HITCHCOCK ( J . Amer. Chem. Soc. 1921,43,1956-1961).- The result obtained by Nelson and Griffin that a given quantity of invertase exhibited the same activity when adsorbed on a solid in the bottom of the reaction vessel as when uniformly distributed throughout the solution (cf. A. 1916 i 516) is not general but repre- sents only a special case. It is now shown that other conditions being equal and the velocity of hydrolysis relatively large the amount of sucrose hydrolysed in a given time is less in the presence of an adsorbent.The decrease in rate is apparently due largely to the uneven distribution of the invertase in the reaction mixture and the extent of the retardation may be considerably diminished by stirring the mixture and thus preventing the settling of the adsorbent Results comparable with those of Nelson and Griffin (Zoc. cit.) are obtained only when the velocity of hydrolysis is relatively small and it is suggested that under these conditions the rate of diffusion of the sucrose to and of the invert-sugar from the enzyme combined with the adsorbent is probably greater than the rate of hydrolysis of the sucrose. The Distinctive Properties of Amylases from Different Sources. JEAN EFFRONT (Compt. rend.1922 174 18-21).- Amylases from different sources may be distinguished from one another by the ratio of their liquefying power to their saccharifying power by the intensity of their saccharifying power by their optimum temperatures by their resistance to temperatures of 7o-1oo0 and by their action a t 20". Some amylases in juices or extracts when heated a t 60" and filtered recover after filtration their activity lost during heating whilst other amylases lose their activity altogether. W. G. T. MERL and J. <DAIMER (2. Unters. Nahr. Genussm. 1921 42 273-290).-A catalase was prepared from the wheat embryo having five times the activity W. G. A Study of the Catalase of Flour.ORGANIC CHEMISTRY. i. 185 of ordinary flour. The optimum hydrogen-ion concentration for the catalase corresponds with p7,=6-2-7.1 ; and the optimum temperature is 3 0 4 0 ' with a temperature coefficient of approxi- mately 1.5.The catalase is relatively resistant to dry heat but extremely sensitive to moist heat. It is less affected by toluene than by alcohol benzene or hydrocyanic acid. [Cf. J. SOC. Chem. Ind. 1922 1 1 4 ~ . ] Decomposition of Amygdalin from the Point of View of Conjugated Fermentation.' J. GIAJA ( J . Chim. Physique 1921 19 77-99) .-The decomposition of amygdalin by emulsin from Helix pomatia and by emulsin from almonds a t 3 7 4 0 " takes place in two stages with intermediate products which are different in the two cases. The fermentation decomposition of amygdalin is not a simple process; the decomposition is a conjugated or coupled fermentation made up at least of two reactions a primary and a secondary fermentation.The decomposition of amygdalin by the above-named emulsins is probably an unique case in which it is possible to follow exactly the progress of both the primary and secondary fermentations. The two actions constituting the couple are within certain limits independent of one another for it is shown that changes in the concentration of amygdalin fer- ment dextrose hydrocyanic acid and benzaldehyde as well as ultra-violet light affect the two reactions differently. The ratio in which the dextrose and hydrocyanic acid appear in the course of the reaction with emulsin from Helix plpomatia varies with the speed of the reaction that is to say with the concentration of the ferment.The more rapid the reaction the more nearly does the ratio approach that in which the dextrose and hydrocyanic acid exist in amygdalin. The influence of the initial concentration of amygdalin on the secondary reaction with both ferments is that the secondary reaction proceeds more rapidly when the initial concentration is small. The influence of an addition of dextrose is different in the case of the two ferments but in both cases it only affects the reaction which produces dextrose. The addition of benzaldehyde and hydrocyanic acid retards the reaction in which these substances respectively are produced. Thus whilst dextrose and hydrocyanic acid affect the fermentation reaction itself benzaldehyde acts on the ferment and destroys it. Ultra- violet rays affect the reaction with emulsin from Helix p m t i a in the sense that the formation of dextrose is more rapid than that of hydrocyanic acid.If the reaction with emulsin from HeEix pomatia is stopped before completion by heating and emulsin from almonds is added it is found that the reaction does not go so far as either ferment alone would have taken it. Thus emulsin from almonds canziot complete the reaction started by emulsin from Helix ponzatia but emulsin from Helix pomatia can complete the rcaction started by emulsin from almonds. Urease. STUEE LOVWLEN (Biochem. 2.. 1021 119 215- 293) .-This paper contains a valuable bibliography of 212 papers and is illustrated throughout with quotations from original papers. A. G . P. J. F. S.i. 186 ABSTRACTS Ol? CHEMICAL PAPERS.The author has carried out experiments covering a wide range of properties of urease but the main portion deals with an attempt to find the time equation which covers the reaction adequately. Van Slyke and Cullen's equation was found not to hold but a simple apparently empirical modification of the unimolecular equation gave excellent results provided that a t each concentra- tion of urea the solution was kept a t the particular optimum PII. H. K. Additive Reactions of Phospho~us Haloids. IT. The Action of tho Trichloride on Saturated Aldehydes and Ketones. J. B. CONANT A. D. MACDONALD and A. McB. KINNEY ( J . Amer. Chem. Soc. 1921 43 1928-1935).-It has previously been shown that benzaldehyde reacts with phosphorus trichloride in acetic acid to give good yields of an a-hydroxyphosphinic acid (cf.&4. 1921 i 69). It is now shown that the reaction can be extendcd to other aldehydes and ketones although with ketones it is of somewhat limited scope and in certain cases it was found desirable to replace the acetic acid by benzoic acid as the medium and work at 150" instead of below 30". The hydroxyphosphinic acids were difficult to isolate in the crystalline state and in some cases could only be obtained as their lead salts. With acetophenone and acetone an unsaturated phosphinic acid was also in each case produced but only isolated from acetophenone. The following new compounds are described a-Phenylvinylphosphinic acid CH,:CPh*PO,H m. p. 112" ; a-hy~roxy-a-methylpropylphosphinic acid isolated as its lead salt ; a-hydroxy-a-ethylbutylphosphinic acid as its lead salt ; cc-hydroxy- aPP-trimethyl~ropylp~sph~nic acid as its lead salt ; a-hydroxy-p- ~hen?ll-u-benzylethylphosphinic acid m.p. 181-182" ; a-hydroxy- a y-diphen ylpropylphosphinic acid m. p. 165-1 68 " ; a- h ydrox y-y- phenyl-a-( p-phen~lethyl)propy~p~os~hinic acid m. p. 173-174" ; a- hydroxydiphenylmethylphosphinic acid m. p. 17 1-172". Additive products could not be obtlained with benzil or anthraquinone. W. G. The Relation between the Modo of Synthesis and Toxicity of Arsphenarnine [ Salvarsan] and Related Compounds. WALTER G. CHRISTIANSEN ( J . Amer. Chem. Xoc. 1921 43 2202- 2210).-The variation in toxicity of diff went samples of salvarsan prepared by reduction of 3-nitro-4-hydroxyphenylarsinic acid by hyposulphite is due to variations in the experimental conditions during the reduction of the nitro-group.To obtain a sample of low toxicity a cold solution of the nitro-compound should be added t o a cold solution of magnesium chloride and sodium hyposulphite with vigorous stirring. The mixture is then rapidly heated at 40" after the addition of vegetable charcoal and filtered the filtrate being rapidly heated a t 55". If the solutions are mixed warm with slow stirring and the mixture only slowly raised to 55" a salvarsan of high toxicity is obtained. For the consistent produc- tion of salvarsan of the lowest toxicity it is advisable to use pure 3-amino-4-hydroxyphenylarsinic acid as the starting material inORGANIC CHEMISTRY. i. 187 which case there is no need to adhere strictly t'o the conditions a t the beginning.This variation in toxicity is apparently general t o the amiiioarylarserio-compounds. It has been found with 3-amino-4 4'-dihydroxyarsenobenzene hydrochloride 3 5 3'-tri- amino-4 4'-dihydroxyarsenobenzene trihydrochloride and 3 5 3' 5'-tetra-amino-4 4'-dihydroxyarsenobenzene tetrahydro- chloride. The variation in toxicity is due to the formation of by-products during the reduction of the nitro-group which unite with the amino-acid in the subsequent reduction of the arsinic acid group giving unsymmetrical arseno-compounds. Arsenated Benzophengne and its Derivatives. W. LEE Lm71s and €1. C. CHEETHAM ( J . Amer. Chem. SOC. 1921,43 2117- 21C)l).-Dichloro-p-arsinobenzoyl chloride condenses quite readily with aromatic hydrocarbons and phenyl ethers in the presence of anhydrous aluminium chloride using carbon disulphide as a solvent. Thus with benzene after warming the product with aqueous sodium hydroxide benzophenone-p-arsenious oxide COPh*C,H,*AsO was obtained which on boiling with water gave benzophenone-p-arsenious acid COPh*C,H,*As( OH) and on oxidation with hydrogen peroxide yielded benzophenone-p-arsinic acid COPh*C,H,*AsO,H giving an oxime.On nitration the arsinic acid gave nitrobenxophenone-p- arsinic acid N0,*C,H,*CO~C,H4*Aso~Hz. Other compounds simi- larly prepared are 4-methylbenxophenone-4'-arse.izious oxide ; 4- methylbenzophenone-4'-arsinic acid ; 4-meihoxybe~~xophenone-4'-arsinic acid ; 4-ethox ybenxophenone-4' -arsinic acid and 4-phenox ybenxophen- one-4'-arsinic acid.p-Carboxyphenylarsinic acid is best obtained for these preparations from p-aminobenzoic acid by Bart's method (Ger. Pat. 250264 and 254345) and subsequently converted into dichloro-p-arsinobenzoyl chloride by Poulenc's method (French Pat. 441215). W. G. 4-Carboxy-2-phenylquinoli1ie-6-arsinic acid. J. R. JOHN- SON and ROGER ADAMS ( J . Amer. Chem. SOC. 1821 43 2255- 2257).-When pyruvic acid is added to a boiling solution of arsanilic acid and benzaldehyde in absolute alcohol and the mixture boiled for four hours 4-carboxy-2-phenylquinoline-6-arsinic acid m. p. 186-187" (corr.) (decomp.) is obtained. It gives a neutral disodium and a slightly alkaline trisodiuin salt a green copper salt yellow silver lead mercurous mercuric and cadmium salts and reddish- 7-Chloro-7 12-dihydro-y-benzophenarsazine and some of its Derivatives.W. LEE LEWIS and C. S. HAMILTON ( J . Amer. Chem. Xoc. 1921 43 2218-2223).-The annexed constitution is considered as probably that of y-benzophen- arsazine. Phenyl-a-naphthylamine reaclily reacts with 14 arsenic trichloride to give 7-chloro-7 12-dihydr0- / b N / v y-benxopheiaarsaxine m. p. 219" which is I I ) physiologically much less irritant than the '\/\/\ / 5 corresponding diphenylchloroarsine. It readily As W. G. brown cobalt and ferric salts. vcT. G . l2 1 /k3 'I 7 reacts with sodium alkyloxides or aryloxidesi. 188 ABSTRACTS OP CHEMICAL PAPERS. to give stable alkyloxy- or aryloxy-derivatives of the type NH<C1b !>ASOR. The following are described 7-Methoxy- 7 12-dihydro-y-benxophenarsazine m.p. 209" ; 7-ethoxy-7 12- dihydro-y-benxophenarsazine m. p. 165" ; 7-n-propoxy-7 12-dihydro- y-benzophnarsaxine m. p. 152" ; 7-n-butoxy-7 12-dihydao-7-benzo- phenarsaxine ; 7-phenoxy-7 12-dihydro-y-benaophenarsazine m. p. 179" ; 7-benzyloxy-7 12-dihydro-y-benxophenarsazine m. p. 154". When oxidised in acetic acid solution by hydrogen peroxide 7-chloro-7 12-dihydro-y-benzophenarsazine gives y-benzophenars- azinic acid NH< 10 !>As(OH) giving a sodium salt. Freshly precipitated silver oxide reacts in ammoniacal solution with 7-chloro- 7 12-dihydro-y-benzophenarsazine to give 7 12-dihydro-y- benzo- phenarsaxine oxide (NH<C10H6>A~),0. The corresponding sul- phide 7 12-dihydro-y-benzophenarsazine sulphide m. p. 204-205" was obtained by bubbling hydrogen sulphide through an alcoholic solution of the chloro-compound.When boiled with an excess of hydrobromic acid 7-phenoxy-7 12-dihydro-7-benzophenarsazine gave 7-bromo-7 12-dihydro-~-benzop~~rs~xine m. p. 227". 7-Iodo- 7 12-dihydro-y-benzophenarsazine m. p. 205" was similarly pre- pared. Diphenylhydrazine when warmed with arsenic trichloride gives 6-chlorophenarsazine. W. G. Organo-derivatives of Bismuth. V. The Stability of Halogen Cyano- and Thiocyano-derivatives of Tertiary Aromatic Bismuthines. FREDERICK CHALLENGER and JOHN FREDERICK WILKINSON (T. 1922,121 91-104). Organo-derivatives of Bismuth. VI. The Preparation and Properties of Tertiary Aromatic Bismuthines and their Interaction with Organic and Inorganic Halogen Compounds. FREDERICK CHALLENGER and LESLIE RANDAL RIDGWAY (T.1922 Aromatic Mercuri-organic Derivatives. The Hofmann Rearrangement and the Nature of Valencies of Mercury in Mercuri-organic Derivatives. MORRIS S. KHARASCH ( J . Amer. Chem. Xoc. 1921 43 1888-1894).-Mercury diphenyl reacts with various acyl halogen amides in dry benzene giving phenyl mercury haloid and the alkylcarbimide the mercury diphenyl thus playing the same part as sodium hydroxide in aqueous solution or sodium ethoxide in absolute alcohol and the amide undergoes the Hofmann rearrangement. Thus with N-bromoacetamide the products are mercury phenyl bromide and methylcarbimide similar changes occurring with N-bromobenzamide and with m-nitro-N-homo- benzamide. On the other hand N-substituted allryl or aryl bromo- and chloro-acetamides do not react with mercury diphenyl any more than they undergo rearrangement with so& urn hydroxide or ethoxidc. The mercury diphenyl thus acts as a base in benzcnr solution being a base of the benzene system in the same way as sodamide is of the ammonium system. C H 6 4 C H C,H (334- 121 104-120).ORGANIC CHEMISTRY. i. 189 Thc author does not coiisider that the clectronia structure for mercury diary1 compounds proposed by Jones and Werner (A. 1918 i 483) has any sound theoretical or experimental basis and proposes as an alternative structure It-Hg-R. The formation of inetallic mercury and beiizyl acetate when mercury diphenyl is hydrolysed by glacial acetic acid at 200" (Jones and Werner ~ O C . cit.) is duc to intramolecular oxidation and recliiction. Mercuri-organic Derivatives. The Mercurisation of Aromatic Arnines and its Relation to the Theory of Substi- tution. MORRIS S. I~ARASCH and ISADORE 31. JACOBSOHN ( J . Amer. Chem. Xoc. 1921 43 1894-1903).-Schoeller Schrauth and Liese (cf. A. 1920 i 120) in their theory of mercurisation assume that the entrance of a group into the nucleus of an aromatic amine is always preceded by substitution on the amino-nitrogen. This theory does not explain however the mechanism of substitu- tion in the case of tertiary amines such as dimethylaniline which contain no replaceable hydrogen. The authors propound the theory that of the aromatic amines only those which are capable of forming salts will mercurise and that mercurisation is always preceded by addition of a mercuric salt to the amino-nitrogen with subsequent rearrangement of the mercury to the ortho- or para-position. This theory also applies equally well without further postulates to the introduction of other groups into the benzene nucleus in the case of aromatic amines. Where such salt formation is not possible as in the quaternary ammoilium salts substitution must take place in the meta-position or as in such special cases as that of mercurisation it is not accomplished a t all. Thus p-nitrodimethylaniline which is an extremely weak base and does not form salts would not mercurise whereas p-nitro- inethylaniline mercurised without difficulty. I n further support of the theory unpublished work is mentioned in which the inter- mediate additive compound from m-nitroaniline and mercnric acetate was isolated. The following compounds are described. o-Nitro-p-acetomy- mc,rcuridimet~?/laia~line In. p. 160" ; o-nitro-p-chloromercv,ridimcth?yE- aniline M. p. 185" (decomp.) ; ~n-ni~ro-p-ac~toxymercz~ric.lim~~7~~~nnilinp m. I). 140" ; m-nitro-p-chlorornercurimethylanilinp rn. p. 220" (decomp.) ; ~-~~itro-o-ncefo.r?/mcrcurimethylaniline r n . p. 197 ' (cleconip.) ; p-nitro-o-chlcromercurinzeth?/Zaniline m. p. 215" (decomp.) ; I'-~i,itro-o-acetoxymcrczcricth?llanililze m. p. 183" ; p-nifro-o-chlom- ?1/Prcurieth?llaizilii~P m. p. 218" (decomp.). For purposes of characterisation 2-bromo-4-?zitrocll~ylan~lin~ m. p. 65-66"; and 2 6-dibromo-4-nitroethyZaiail~ne m. p. 75-'iG0 werc prepared by brominating p-nitroethylaniline in acet,ic acid An Indirect Method of Preparation of Organic Mercuric Derivatives and a Method of Linking Carbon to Carbon. MORRIS S. KHARASCH ( J . Amer. Clzem. Soc. 1921,43,2238-2243).- When mercuric salts of certain carboxylic acids are heated carbon t + - - W. G. solution using the requisite proportions of bromine. w. G.i. 190 ABSTRACTS OF CHEMICAL PAPERS. dioxide is split off and the mercury takes the place originally occupied by the carboxyl group. Thus mercuric 2 4-dinitro- phenylacetate when heated a t 180" gives mercury 2 4 2' 4'- tetranitrodi benxyl C,H,( N O,),*CH,*Hg*CH,*C,H,( NO,) m. p. 235" ; and mercuric 2 4 6-lrinitrobenzoate gives mercury 2 4 6 2' 4' 6'- hexanitrodiphenyl M. p. 273". The latter compound when heated in alcohol with mercuric chloride gives 2 4 6-trinitrophenyl mercuricldoride C,H.#O,),*HgCl m. p. 202" which when treated in aqueous suspension with iodine in potassium iodide solution gives 2 4 6-trinitroiodobenzene and a compound which is prob- ably 2 4 6 2' 4' 6'-hexanitrodiphenyl. It is thought that by heating these mercury compounds in the dry state or in some solvent the mercury would oxidise one of the carbon atoms and thereby link the two carbon atoms together. This was observed in the case of 2 4 2' 4'-tetranitromercurydibenzyl tetranitro- dibenzyl being obtained. This work is being extended to mercury salts of various types of carboxylic acids. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9222200101

出版商:RSC    

年代:1922

数据来源: RSC

摘要:

ii. 140 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Separation of the Element Chlorine into Isotopes (Isotopic Elements). The Heavy Fraction from the Diffusion. WILLIAM D. HARKINS and ANSON HAYES (J. Amer. Chem. Soc. 1921 43 1803-1825).-By means of elaborate diffusion a definite increase in thc atomic weight of chlorine has been obtained. The increase in atomic weight amounts in different experiments to from slightly less than to considerably more than one part in a thousand (1 in 645). The diffusion experiments were effected with hydrogen chloride and a considerable amount of the isotopic acid has been obtained. The separation of isotopes by diffusion is discussed in terms of the Rayleigh diffusion equation which applies to the diffusion into a vacuum. It is shown that for a high efficiency the pressure of the gas on both sides of the diffusion wall should be low first to secure good mixing and secondly to insure that the passage through the porous partition shall be entirely molecular.A rapid and precise method for the determination of the atomic weight of isotopic chlorine has been devised. It is found that in the separation of isotopcs the percentages of the different isotopes present are as important factors as the atomic weight differences. Thus contrary to what has been supposed it is shown even aside from the greater difficulties involved in obtaining and handling neon that it is easier to produce a small increase in the atomic weight of chlorine (of the magnitude of 0.05 unit) than to produce the same increase in the atomic weight of neon.Viscosities of the Hydrogen Haloids. H. HARLE (Proc. Roy. Xoc. 1929 [A] 100 429-440).-The viscosity of hydrogen chloride bromide and iodide has been determined by the method of transpiration through a capillary tube. Measurements were made a t temperatures in the neighbourhood of 20" and lOO" and from the results the viscosity is calculated for 0" and 100" rc- spectively. The following values in C.G.X. units are recorded hydrogen chloride yo= 1.332 x ; vlo0= 1.837 x lo4 ; hydrogen bromide yo= 1.710 x ; 17roo=2*365 x lo-* ; hydrogen iodide qo= 1.731 x The values of C the Suther- land const.ant are 357 375 and 390 for the three gases respectively. J. I?. S. q,00=2*403 x low4. J. F. S. Numerical Revision of the Data referring t o the Density of Gaseous Hydrogen Bromide Atomic Weight of Bromine.E. MOLES ( J . Chim. Physique 1921 19 135-138).-The molecular weight of gaseous hydrogen bromide with reference to oxygen has been calculated to be 80.944 and from this the atomic weight of bromine is 79.936. If however the value for the weight of the normal litre of oxygen recently published (cf. following abstract) is used the atomic weight of bromine becomes 79.927. J. F. S.INORGANIC CRER.IISTRY. ii. 141 Critical Study of the Modern Value of the Density of Gaseous Oxygen. E. MOLES ( J . Chim. Physique 1921 19 100-120).-A discussion of the modern results for the density of oxygen leads t o the value L,=1~42891&0~00003 as the most prob- able value for the weight of the normal litre of oxygen.The value is deduced from 162 measurements made by nine workers using oxygen obtained from three different sources and by three essentially different methods. If only the most recent measurements by weighing a globe of the gas are considered the mean is Lo=1.42894. Up to this the value accepted was 1.42905 which can no longer be maintained and although the difference is only 1 in 10,000 yet it cannot be neglected in the calculation of molecular weights. It is proposed that the value 1.42891 be accepted as the standard and this in some cases may be rounded to 1.4289. If this value is calculated to the conventional value of 9 y=980%65 C.G.S. units then the value of LON becomes 1.42897 which may be rounded to 1.4290. J. I?. S. Solubility. VII. Solubility Relations of Rhombic Sulphur.JOEL H. HILDEBRAND and CLARENCE A. JENKS ( J . Amer. Chem. SOC. 1921 43 2172-2177).-The solubility of rhombic sulphur has been determined in carbon tetrachloride benzene toluene nz-xylene heptane and ethylene dichloride a t 0" 25" 35" 45" and 54". The results are expressed in molecules of S per 100 molecules of solvent and in grams per 100 grams of solvent. The following values in grams per 100 grams of solvent are recorded Carbon tetrachloride 0" 0.339 ; 25" 0.831 ; 35" 1.155; 45" 1.564; and 54" 2.005; heptane 0" 0.124; 25" 0.362; 35" 0.512; 45" 0.698; and 54" 0.926; toluene 0" 0.897; 25" 2.018; 35" 2.722; 45" 3.620; and 54" 4.85; m-xylene 25" 1.969; 45" 3.604; benzene 25" 2.074; 54" 5.P65; ethylene di- chloride 25" 0.826; 40" 1,380; 79" 5.43; and 97*5" 9.97.It is shown that with the exception of certain minor discrepancies the solubilities of sulphur accord well with the internal pressure relations of the substances involved. J. P. S. The Constitution of Selenium. H. PBLABON (Compt. rend. 1921 173 1466-1468).-The grey selenium previously described (cf. A. 1921 ii 533) the specific resistance of which may vary from a few ohms to several million ohms is now shown to consist of two modifications. The a-modification has a very high resistance and is prepared by heating selenium a t a temperature only just above its melting point and then allowing it to cool slowly. The specific resistance of this modification diminishes a t first very rapidly with rise in temperature and then more slowly. At 200" the resistance is about 70,000 ohms and at 218" the substance melts the melting being accompanied by a sudden rise in resist'ance. The p-modification has a very small specific resistance.It is obtained by maintaining the molten selenium at a temperature near its boiling point for some time and then allowing it to cool. The p-modification is not stable a t low temperatures and it isii. 142 ABSTRACTS OF CHEMICAL PAPERS. readily changed into the a-form by oscillations of its temperature between 15" and 200". Influence of Freezing on Colloidal Selenium. 11. A. GUTBIER FR. HEINRICH and J. HUBER (KoZEoid Z. 1921 29 287-293; cf. A 1921 ii 693).-A continuation of work previously described (Eoc. cit.) on the effect of freezing on selenium sols. Three new series of experiments are now described in which it is shown that the sensitiveness of undialysed selenium sols prepared by means of sulphur dioxide towards cold increa'ses with the time during which they are frozen. The system may be frozen for short periods and will then melt to form a typical colloid but more pro- longed freezing increases the tendency to coagulate to irreversible gels on melting and very prolonged freezing will even cause coagul- ation to take placc in the solid.I n this respect there is no funda- mental difference between dialysed and undialysed sols but the dialysed system is somewhat more sensitive. The reducing action of sulphur dioxide on solutions of selenious acid is retarded by freezing the mixture. If the mass is kept frozen for a long time the colloid is precipitated in the ice and thereby the reduction process is accelerated.The precipitation appears to exercise it nucleus action by which the reduction in the solid mass is acceler- ated so that eventually more selenium is precipitated in the frozen mass than would be produced in a solution in the same time. In general the coagulation in the frozen sol commences where the sol is in contact with the air as is shown by the formation of a coloured ring on the upper surface of the ice. When test-tubes are used for the experiments the curved lower portion of the tube always shows an increased concentration of selenium. The form of the vessel in which the freezing takes place is shown to exert an influence on the coagulation. When a sol is poured on ice and frozen it is found that the disperse phase diffuses into the ice.It has been W. G. found scarcely possible to" freeze selenium sols in capillary tubes. J. I?. S. Metallurgy of Tellurium by the Wet Way. PIERRE HULOT (BUZZ. SOC. chim. 1921 [ivl 29 107Q-l071).-The method of reduction of potassium anhydrotellurate by zinc and hydrochloric acid with the precipitation of metallic tellurium (cf. A. 1920 ii 174) is modified by using aluminium and sodium or potassium hydroxide for the production of nascent hydrogen with the result that the reduction is completed in one hour instead of ten. The aluminium must be pure and free from copper. Manganese in the Catalytic Oxidation of Ammonia. CHARLES SNOWDEN PIGGOT (J. Amer. Chern. Soc. 1921,43 2 0 3 G 2045).-The action of manganese dioxide alone and when mixed with copper oxide or silver oxide and various alloys of manganese copper silver iron and silica as catalysts in the oxidation of ammonia have been investigated.A mixture of manganese dioxide with 40% of copper oxide a t 800" is shown to have an efficiency of more than 90%. All the substances mentioned catalyae the W. G.INORGANIC CHEMISTRY. ii. 143 oxidation of ammonia with various efficiencies which with suitable conditions are about 50%. The physical structure of the oxide catalyst is of great importance extremely fine subdivision giving a large adsorbing surface with very small pores being conducive to greater activity. J. F. S. Attempt to Prepare Nitro-nitrogen Trichloride. 11. Behaviour of Mixtures of Nitrogen and Chlorine in a Flaming Arc.WILLIAM ALBERT NOYES (J. Arner. Chem. SOC. 1921 43 1774-1782; cf. A. 1913 ii 584).-Attempts to prepare nitro- nitrogen trichloride or nitrogen trichloride by passing mixtures of nitrogen and chlorine through a flaming arc were entirely un- successful. Passing the same gases through a powerful ozoniser had the same result and no action at all occurred with Strutt's active nitrogen. The results although negative confirm Lewis's hypothesis that electrons are held jointly by two atoms rather than the view that electrons are transferred from one atom to another when atoms combine. J. F. S. Vapour Pressures of Aqueous Solutions of Nitric Acid. WILLIAM C. SPROESSER and GUY B. TAYLOR (J. Amer. Chern. SOC. 1921 43 1782-1787).-The total and partial vapour pressures of nitric acid solutions of the concentrations 20% 40% 56% 68% and SOY0 by weight have been measured a t temperatures 0" 35" 50" 65" and 80".From the data the vapour pressure for each 10% increase in concentration and each 10" rise in temperature has been calculated and tables drawn up. Attempts to measure the vapour pressure of 90% acid were unsuccessful owing to the decomposition of the acid at all temperatures except 0". J. F. S. Reducing Actions of Arsenious Acid. MORITZ KOHN (Monatsh. 1921 42 221-226) .-When copper sulphate is heated with ammonia solution and arsenious anhydride in a sealed tube in a boiling water-bath it undergoes reduction to cuprous salt with formation of arsenic acid. After the resulting cuprous solution has been oxidised to the cupric condition by atmospheric oxygen estimation of the arsenic acid reveals more of the latter than corre- sponds with the equation 2Cu"+As0,"'+20H'=H,O+ 2Cu'+ As04"'.Evidently oxidation of the ammoniacal cuprous solution to the cupric stage activates the atmospheric oxygen for the oxidation of the residual unchanged arsenious acid. Depression of the con- centration of hydroxyl ions by addition of ammonium salts retards the reduction of cupric to cuprous salt. Catalysis in the Interaction of Carbon with Steam and with Carbon Dioxide. HUGH STOTT TAYLOR and HARVEY A. NEVILLE ( J . Amer. Chem. SOC. 1921 43 205&2071).-The effect of potassium carbonate sodium carbonate lithium carbonate barium carbonate calcium carbonate sodium chloride ferric oxide copper sodium silicate borax and nickel as catalysts on the interrtc- tion of steam on carbon has been investigated using various forms of T.H. 9.ii. 144 ABSTRACTS OF CREMICAL PAPERS. carbon. It has been discovered that the interaction of carbon and carbon dioxide is likewise accelerated by the presence of the same materials and a striking parallelism between the catalysts for the two reactions has been shown. The probable mechanism of the steam-carbon reaction has been investigated. It has been shown that good catalysts for the water-gas reaction for example iron oxide are ineffective in the steam-carbon and carbon dioxide- carbon reactions. Catalysis of the water-gas reaction thus being excluded from consideration it has been shown that the acceleration of the reaction C+C02=2C0 and therefore the acceleration of the reaction C+ 2H,O = C0,j- 2€I may be ascribed to increased ad- sorption of carbon dioxide by the carbon surfaces in presence of active catalytic agents.Adsorption measurements confirm this view. The results have been considered in connexion with the suggested existence of a surface complex C,O and have been found to agree witch this conception. J. F. S. A Modification of Silicon Soluble in Hydrofluoric Acid. WILHELM MANCHOT (Bey. 1921 54 [B] 3107-3111).-Moissan and Siemens (A. 1904 ii 560) have isolated specimens of silicon from a silver regulus which suffer loss of weight (up to 99%) when treated with hydrofluoric acid and subsequently Lebeau (A 1906 ii 168) has brought forward evidence to show that a similar modification is present in copper-silicon alloys rich in the latter.The substance however does not appear to have been investigated Considerable difficulty is experienced in preparing silicon which is completely resistant towards hydrofluoric acid ; the product obtained by Wohler's method requires frequently repeated treat- ment with the acid before a stable specimen is secured. It is shown that an appreciable gain in weight occurs when the latter is melted with silver in an electric furnace in an atmosphere of air oxygen or carbon monoxide but this is in itself insufficient to account for the subsequent solubility of the silicon. The latter however is only produced in the soluble condition when the regulus is suddenly cooled. The silver may be replaced by aluminium.It dissolves in hydrofluoric acid with evolution of hydrogen. It is remarkable that Moissan and Siemens describe their product as exactly resembling crystalline silicon whereas the author's specimens are dark to pale brown and amorphous; they leave a pale brown powder after being treated with hydrofluoric acid. fully . H. W. Organogels of Silicic Acid. B. S. NEUHAUSEN and W. A. PATRICK ( J . Amer. Chem. Soc. 1921 43 1844-1846).-Hydrogels of silicic acid have been repeatedly soaked in alcohol acetone and benzene for long periods dried in a vacuum of 5 mm. a t SO" 120° and 270" successively for periods of one hour and analysed. The dried products contain alcogel 4*23y0 water 3'90y0 alcohol ; acetone gel 4.77% water 3'75y0 acetone ; benzene gel 4.31y0 water 3.82% benzene.Hence it follows in opposition to Graham'sINORGANIC (3HEMISTRY. ii. 145 statement that the water of a hydrogel of silicic acid cannot be entirely replasced by a second solvent. It has been previously shown that heating silicic acid gels in a vacuum at 300" for six hours does not reduce the water content below 4%% a quantity which is very near the amount of water left in the organo-gel above and indicates that this water is very firmly combined in the gel. J. F. S. Relative Densities of Alkali Metal Amalgams and Mercury. 11. EDGAR C. BAIN and JAMES R. WITHROW ( J . Physical Chem. 1921 25 535-544; cf. A. 1916 ii 431).-The methods of for- mation and the relative densities of liquid and solid amalgams of sodium potassium ammonium and calcium have been inves- tigated.It is shown that solid amalgams float on the mother- liquor and do not sink as stated by Kerp (A. 1898 ii 516). The method used by Merp (Zoc. cit.) produces sodium and potassium amalgams which are like the amalgams produced by other methods inasmuch as the solid is lighter than the liquid. Oily and pasty amalgams are due to fine crystals incorporated in the liquid. By electrolysis of solutions of potassium chloride amalgams with concentrations up to 2.31:/ of potassium were obtained. No difficulties except those of collection and preservation were met with in the production of ammonium amalgams by the electrolysis of solutions of ammonium chloride but crystalline amalgams cannot be obtained in this way. Electrolysis of an acidified solution of calcium acetate is not a satisfactory method for the production of calcium amalgams but it does produce a dilute calcium amalgam. J.F. 8. The Production of Potassium Hydrogen Sulphate from Ammonium Hydrogen Sulphate and Potassium Sulphate. W. DOMINIK (Przemysl Chem. 1921 5 10-15 3 7 4 0 63-67).-- Reaction in the presence of steam superheated a t 200-400" takes place according to the equation M,S0,+NH4HS0,=2MHS04+ NH,; lack of steam results in the production of pyrosulphates. In the above reaction K=[MHS04]2/[M,S0,] . [NH,HSO,] increases with the temperature according to a logarithmic function. Theor- etical consideration is given to the use of a mixture of sodium and potassium sulphat,es in the reaction. CHEMICAL ABSTRACTS. Crystal Structures of Sodium Chlorate and Sodium Bromate.ROSCOE G. DICKENSON and ELBRIDGE A. GOODHUE ( J . Amer. Chem. Xoc. 1921 43 2045-2055).-A large amount of X-ray spectrometer data for sodium chlorate and bromate has been obtained and tabulated. In agreement with other observers it has been found that the nature of the crystal surface has a considerable effect on both the absolute and relative inten- sities of reflection. The ease with which reflections from one face may be mistaken for those from another and the necessary precautions to avoid this have been pointed out. It is shown that the atoms in sodium chlorate and sodium bromate are veryii. 146 ABSTRACTS OF CHEMICAL PAPERS. probably arranged with the symmetry of the Schonflies space group T4 all oxygen atoms being equivalent. Sets of positions of the atoms in the unit structure only slightly different for the chlorate and bromate have been suggested.J. F. S. Preparation and Study of the Rarer Alkali Bromates. Rubidium Bromata. HAROLD D. BUELL and C. R. MCCROSICY ( J . Amer. Chern. Xoc. 1921 43 2031-2034).-Rubidium bromate was prepared by treating the pure carbonate with a n excess of bromic acid and recrystallising the product (cf. -4. 1920 ii 688). The following figures are the solubilities in 100 grams of water a t various temperatures 25" 2.93; 30" 3.55; 35" 4.28 and 40" 5.08. The corresponding figures for cmium bromate are 25" 3.66; 30" 4.53; 35" 5.32. The following melting points are recorded potassium bromate 405" ; czesium bromate 420" ; rubidium bromate 430". Both rubidium and czesium bromates form small cube-like crystals which however belong to the hexagonal system ; they have a refractive index between 2.144 and 2.22.J. F. S. Vapour Pressure of some Salts. 11. H. VON WARTENBERC and H. SCHULZ (2. Elektrochem. 1921 27 568-573; cf. Albrecht and Wartenberg ibid. 162).-Using the method previously employed the authors have determined the vapour pressures of lithium chloride czesium chloride rubidium chloride lithium bromide cmium bromide rubidium bromide sodium fluoride potassium fluoride lithium fluoride czsium fluoride rubidium fluoride sodium iodide cmium iodide and rubidium iodide. The measurements were carried in most cases up to the boiling point of the salt in question. The following data are recorded pressures being in atmospheres lithium chloride b.p. 1382" m. p. 606" log p= -37200/4*57T+4*923 ; czsium chloride b. p. 1303" m. p. 626" logp= -37400/4.57T+5.190; rubidium chloride b. p. 1383" m. p. 717" logp= -37800/4*57T+4*998; lithium bromide b. p. 1310" m. p. 549" logp= -35600/4.57T+ 5.109; cssium bromide b. p. 1300° m. p. 627" logp= -36750/4*5717+5*113 ; rubidium bromide b. p. 1350" m. p. 681" log p= -36980/4.5711+4*964 ; sodium fluoride b. p. 1695" m. p. 988" log p= -56600/4*57T+6.299 ; potassium fluoride b. p. 1505" m. p. 846" logp= -41900/4*57T+5*138 ; lithium fluoride b. p. 1676" m. p. 842" logp= -55100/4-5713+6.190; czsium fluoride b. p. 1251" m. p. 684" logp= -34700/4.57T+ 4.982; rubidium fluoride b. p. 1410" m. p. 775" logp= -40000/4.57T+5*243 ; sodium iodide b. p. 1300" log p= -37000/4*57T+5.130 ; lithium iodide b.p. 1170" log p= -40300/4-57T+6*105 ; caesium iodide b. p. 1280" log p= -36600/4*575!'+5*165 ; and rubidium iodide b. p. 1305" log p= -37000/4*5711+5*148. The results show that the heats of for- mation of the haloids of potassium rubidium and czesium lie very close together whilst that of the lithium salts is much higher and that of the sodium salts much lower. J. F. S.INORGANIC CHEMISTRY. ii. 147 Catalytic Influence of Foreign Oxides on the Decomposition of Silver Oxide Mercuric Oxide and Barium Peroxide. JAMES KENDALL and FRANCIS J. FUCHS ( J . Amer. Chem. Xoc. 1921 43 2017-2031).-The effect of foreign oxides on the temperature and rate of decomposition of silver oxide mercuric oxide and barium peroxide under an oxygen pressure of one atmosphere has been experimentally investigated.In almost all the systems examined the added oxides (CuO IVTiiO Fe203 CeO SiO CrO,) induce a considerable change in the decomposition temperature. Most commonly there is a marked lowering in this point; thus quoting an extreme case an equirnolecular mixture of barium dioxide and cupric oxide has an oxygen equilib- rium pressure of 1 atm. at 322" a temperature which is approxi- mately 500" below the decomposition temperature of pure barium dioxide. I n a few systems a comparatively small rise in the decomposition temperature is indicated. In all cases however the rate of oxygen evolution is markedly increased. The decompo- sition temperatures recorded refer to true equilibrium conditions concordant values being obtained with rising and falling tempera- ture.The results are tentatively ascribed to the formation of unstable intermediate compounds between the two oxides present. The increased rates of decomposition may be referred to adsorption effects but the large temperature changes point strongly to the actual participation of the added oxide in the reaction. Direct evidence was given in certain mixtures of the production of stable complexes. J. F. S. Physical Chemistry of the Oxides of Lead. 111. Hydrated Lead Monoxide. SAMUEL GLASSTONE (T. 1922 121 58-66). Reactions in Fused Salt Media. I. Basic Lead Chromates. J. F. G. HICKS ( J . Physical Chem. 1921 25 545-560).-The reaction between lead monoxide and sodium chromate in fused sodium chloride and a 50% mixture of sodium and potassium nitrates has been investigated and the equilibrium diagram of the system PbO-PbCrO constructed.It is shown that reactions in fused salts can be brought about in such a way as to yield products analogous to those prepared from the same initial sub- stances in aqueous solution. The chief difference between these reactions and their analogues in aqueous solution lies in the smaller velocity of the former probably due to the relative insolubility of the reacting substances in the fluxes as compared with water. There is in several cases a reaction between the flux and the dis- solved substance similar to hydrolysis. This analogy would appear to indicate that these solvolytic reactions are ionic but the second phase of the reaction forming basic lead chromates points to a non-ionic reaction.It may be a purely molecular (additive) reaction resulting in the formation of compounds of higher orders. Such a conclusion explains satisfactorily the slow- ness of the reactions aside from the low solubility of the solutes in the fused salt medium. Whilst at least one basic lead chromate,ii. 148 ABSTRACTS OF CHEMICAL PAPERS. PbO,PbCrO may be prepared by alkaline hydrolysis it does not follow that the basic lead chromates formed in fused salt media are formed by an entirely analogous process. Two new basic chromates have been prepared by the present method which have not been obtained by the wet process; these have the formulze 2PbO,PbCrO and SPbO,PbCrO respectively. A fourth compound Pb0,2PbCr04 is readily prepared by the fusion process and has been stated to be formed by the wet process but the author has been unable to prepare it by this method.The existence of the four basic lead chromates named is confirmed by the equilibrium diagram of the system PbO-PbCrO,. Other basic lead chromates described in the literature are shown to be mixtures or solutions of the compounds named above in one another. Salts of ortho- chromic acid are shown not to exist; whilst the salt Pb,CrO may be the salt of the monohydrate of ordinary chromic acid it could equally well be a true basic salt or a compound of a higher order so far as the present work is concerned. At the temperature (225-800") the stable form of lead monoxide is yellow in colour. This combining with yellow lead chromate yields red compounds all of which point to compounds of a higher order.The red com- pound formed by alkaline hydrolysis of normal lead chromate could well be considered. a basic salt but the addition of lead oxide and lead chromate molecules to form a compound of higher order might as easily take place in aqueous solution as in the nitrate flux used to form a compound of very closely the same composition. The reddening of lead monoxide in the nitrate flux has been shown to be due to change in crystalline form and not as might be supposed to the formation of red lead. Reduction of Copper Oxide by Hydrogen. ROBERT N. PEASE and HUGH STOTT TAYLOR ( J . Amer. Chem. Soc. 1921 43 2179-2188).-An investigation of the characteristics of the reduction of cupric oxide by hydrogen and the effect on the reaction of adding metallic copper to the oxide and water vapour and oxygen to the hydrogen has been carried out.It is pointed out that the reaction is auto-catalytic copper being the auto-catalyst. The reaction appears to take place a t the copper-copper oxide interface. This is shown by the character of the reduction curve and the fact that the addition of metallic copper accelerates the reaction. It is shown that the presence of water vapour in the hydrogen markedly interferes with the formation of the original copper nuclei from which the reaction zone that is the copper- copper oxide interface spreads out ; it does not markedly affect the subsequent reaction a t the interface however. The presence of oxygen in the hydrogen strongly inhibits the reaction a t the interface but in all probability has no marked effect on the primary reaction that is the formation of the original copper nuclei.J. F. S. J. F. S. The Oxidising Properties of Sulphur Dioxide. 111. WILLIAM WARDLAW and FREDERICK WILLIAM Copper Chlorides. PINKARD (T. 1922,121 210-221).INORGANIC CHEMISTRY. ii. 149 Behaviour of Ammoniacal and Alkaline Copper Solutions. MORITZ KOHN (Monatsh. 1921 42 83-87).-When arsenic is heated in a sealed tube with ammoniacal copper solution the cupric compound undergoes reduction first to cuprous salt and subsequently to copper 3Cu**+As+30€I'=AsO,'''+3Cu'+3H' and 3Cu'+ As+3QH'= AsQ,"' + 3Cu+ 3H' ; the copper liberated unites with the excess of arsenic to form greyish-black copper arsenide.Exactly similar changes occur when antimony is heated with ammoniacal copper solutions containing tartaric acid the solid deposited being then reddish-black and containing the copper and the excess of antimony. With bismuth and ammoniacal copper solutions containing tartaric acid rapid action occurs but the reduction proceeds only as far as the cuprous compound. Alkaline solutions of copper salts such as Fehling's solution or an aqueous solution containing copper sulphate glycerol and potassium hydroxide are rapidly reduced by arsenic antimony or bismuth with separation of copper 2As( 2s b) + 3Cu" + 60H'== 2As0,( Sb 0,)"' + 6H'+3Cu or 2Bi+3Cu"= 2Bi'" +3Cu. T. H. P. Separation of the Isotopes of Mercury. J. N. BXONSTED and G. VON HEVESY (2. physikal. Chem.1921 99 189-206 and Phil. il!Iag. 1922 43 [vi] 31-49).-A partial separation of the isotopes of mercury has been achieved by two processes. (1) Evaporation method (ideal distillation) based on the difference in the velocities of evaporation OP the isotopes. The distillate was found to be richer and the remainder poorer in the lighter isotope than the original substance. (2) Effusion method. A fraction of the mercury vapour pcnetrates through narrow openings into a condensation chamber where the lighter isotope is found in a relatively larger amount than in ordinary mercury. The results of the experiments agree with the hypothesis according to which the evaporation as well as the effusion velocity of the isotopes is inversely proportional to the square root of their molecular weights ; they are further in conformity with Aston's results obtained by means of mass spectrographic observations.The partial separation achieved was proved by measurements of density. The density difference found between the heaviest and lightest mercury amounts to O-49q(3 corresponding wit,h a difference of 0.1 unit in the atomic weight of mercury. Physico-chemical Analysis of Aluminium Oxy-salts and Aluminium Oxide Sols. MONA ADOLF WOLFGANG PAULI [with FRANZ JANDRASCHITSCH] (Kolloid z. 1921 29 281-287; cf. A. 1017 ii 563; 1921 ii 700).-The composition and nature of aluminium oxy-chloride sols have been investigated by means of measurements of the concentration of hydrogen and chlorine ions the total chlorine concentration and the electrical conductivity. A number of transport determinations have also been made.It is shown that it is impossible to remove all the chlorine from the products of hydrolysis of aluminium chloride by washing. A quantity of chlorine which is greatly in excess of that contained J. F. S.5. 150 ABSTRACTS OF CHEMICAL PAPERS. in the hydrochloric acid required for peptisation always remains. On boiling well washed aluminium hydroxide with dilute hydro- chloric acid sols of various compositions are obtained up to a limiting composition represented by the formula [Al(OH),],,AlOCl. Of these two have been investigated. Aluminium oxy-dichloride AlCl,*OH behaves as a ternary electrolyte and on dilution is strongly dissociated the brocess being complete a t a dilution 0.00106N.This compound shows a remarkably small hydrolysis which amounts to 0.1% at 0*068N and in a 0.00106N solution is only 0.25%. The compound alumiiiyl monochloride Al( OH),Cl or AlOC1 behaves as a binary electrolyte. The conductivity data indicate that a complex ionisation OCCUI"~ in this case of the type Al( OH),ClIAlO indicating a compound in which one aluminium atom of the complex acts as the central atom of a negative complex whilst the other furnishes a stable univalent positive ion. The peptisation of aluminium hydroxide leads to a sol of the composi- tion 2[A1( OH),]Al( OM),Cl and this on dilution undergoes complex ionisation represented by the formula? (1) 10A1( OH),,4A1OC1,A1O~Cl; (2) 12Al(QH),,5AlQCl,AlO~Cl ; (3) 16A1(OH),,7Al0C1,A10~Cl. On the other hand no complex ionisation of the form Al(OH),IAlO has been observed in the case of aluminium hydroxide.J. F. S. Germmiem. I. Extraction from Germanium-bearing Zinc Oxide. Non-occurrence in Samarskite. L. M. DENNIS and JACOB PAPISH ( J . Amer. Chem. Xoc. 1921 43 2131-2144).- A method of extracting germanium residues obtained in the smelting of certain American zinc ores has been investigated and is described. The residue contains zinc oxide considerable quanti- ties of lead arsenic and cadmium and small quantities of indium tin and antimony in addition to the germanium. A kilogram of the crude oxide is placed in a 5-litre Pyrex flask which is fitted with a two-holed rubber stopper carrying a bent glass tube for connexion to a Liebig condenser and a second short glass tube for introduction of the acid. The condenser leads under the surface of water contained in a 4-litre bottle which acts as receiver.Two and a half litres of hydrochloric acid (d 1.18) are added to the ore and the flask is heated until 2 litres of distillate have been collected. The distillate at this point contains all the germanium and a great deal of the arsenic from the ore. The distillate is poured into a 15-litre bottle until 10 litres have been accumulated carefully acidified with sulphuric acid until it is 6N (this must be carefully done to prevent loss of germanium chloride) and treated with washed hydrogen sulphide. The precipitate is at first yellow due to arsenic but later becomes whiter due to the germanium. When precipitation is complete the bottle is stoppered and kept for twenty-four hours.The solution is filtered by suction and washed with 3N-sulphuric acid which has previously been saturated with hydrogen sulphide. The filtrate is kept for forty-eight hours when usually a small quantity of a white precipitate (corresponding with 2 mg. of germanium) separates the majority of the super- natant liquid is siphoned off and the small amount of liquid andINOBGTANIC CHEMTSTkEP. ii. 151 precipitate worked up with the filtrate from the next lot of pre- cipitate. At this point two different methods of procedure are possible. (1) The moist sulplzides are added to hot 50% sodium hydroxide until a small quantity remains undissolved; this is then just dis- solved by the addition of a little more sodium hydroxide.The solution is made strongly alkaline by the addition of 8 grams of solid sodium hydroxide and placed in a large Pyrex flask fitted with a rubber stopper carrying a delivery tube a separating funnel and a glass tube reaching almost to the bottom of the flask. The flask is connected to a condenser and receiver as before. Washed chlorine is passed in to oxidise the arsenic to the quinquevalent condition. When the solution is saturated with chlorine the rate of entry of the chlorine is reduced and concentrated hydrochloric acid is added in large excess from the funnel. The flask is heated until half the liquid has distilled. The germanium chloride passes over and is hydrolysed by the water in the receiver forming white hydrated germanium dioxide. Should oily drops form in the re- ceiver more water is added to reduce the acid concentration and so allow the hydrolysis to proceed.The receiver is now replaced by a second one the distilling flask is filled up again with con- centrated hydrochloric acid and the distillation continued as before. Most of the germanium chloride passes over in the first distillation but for a complete separation the distillation must be repeated several times. The hydrated oxide is filtered washed first with dilute sulphuric acid and then with water and dried a t 110". It is pure white and contains traces of sodium calcium and iron but no arsenic. The filtrates from the hydrated oxide are treated with hydrogen sulphide and the germanium sulphide is recovered. The impurities mentioned are removed by dissolving in a slight excess of sodium hydroxide saturating with chlorine and distilling with hydrochloric acid hydrolysing the distillate as before.(2) This process is generally superior to the former in its greater economy of reagents. The wet sulphides are washed with 3N- sulphuric acid until free from chlorine and dried a t 110". They are then roasted in shallow iron dishes a t temperatures not exceed- ing 500". The roasted material is dissolved in sodium hydroxide (50%) chlorinated and distilled with twice its weight. of concentrated hydrochloric acid. A repetition of the distillation removes the last trace of arsenic. Either process gives a very pure germanium dioxide ; the yield is better by the first but the second is more rapid and economical. Germanium in ores is estimated by grinding 20-100 grams of the finely ground dried and weighed ore into a paste with water and pouring into a solution of sodium hydroxide in a hard flask the proportions being 2 of ore 1 sodium hydroxide 5 of water.The flask is fitted with a delivery tube for leading in chlorine a fraction- ating column and a small tap funnel. It is connected with a Liebig's condenser which leads to two Erlenmeyer flasks in series containing water to the depths of 3 cm. and half full respectively. The receivers are cooled with ice. The distilling flask is surrounded This removes a great deal of the arsenic.ii. 152 ABSTRACTS OF CHEMICAL PAPER& by ice and the contents are saturated with chlorine; the solution is then neutralised by hydrochloric acid and an excess equal to twice the weight of the ore added.The ice is removed and a slow distillation in chlorine carried out until one-half the liquid in the flask has passed over. An equal volume of hydrochloric acid is added to the distilling flask and the distillation continued until its volume is again reduced by one-half. This is then repeated once more. The receivers are disconnected acidified with sulphuric acid to make the solutions 6N saturated with hydrogen sulphide and kept for twenty-four hours. In a successful experiment there will be no germanium in the second flask. The precipitate is brought on to an ashless paper and washed with 327-sulphuric acid saturated with hydrogen sulphide until free from chloride then washed with alcohol to remove the acid and dried.The bulk of the precipitate is placed in a porcelain crucible and dried moistened with 1 1 nitric acid and warmed to drive off all the liquid allowed to cool treated with concentrated nitric acid dried and ignited. The filter-paper is incinerated in a second crucible treated with concentrated nitric acid and ignited. The filtrate from the ger- manium sulphide is kept forty-eight hours and the small precipitate formed filtered and treated as above. The weight of the germanium dioxide in the crucibles represents the germanium in the ore. Using this method the amount of germanium in the material used for the extraction of germanium was found to be sample I 0-247% sample I1 0.19%. Samarskite has been analysed by this method and found not to contain germanium.ARNE WESTGREN and AXEL E. LINDH (2. p7ysikal. Chem. 1921 98 181-210).- Various types of iron and steel have been subjected to Rontgen ray spectrographic examination. It is shown that the results of Hull (Phys. Review 1917 9 84 10 661) that pure iron a t ordinary temperatures (a-iron) possesses a space-centred cubic lattice is in keeping with the present work. At 500-836" that is within the so-called p-iron region the atoms are groupcd in exactly the same way as in a-iron. Since in the authors' opinion allotropy and polymorpliy are synonymous @-iron can only be regarded as a particular modification of a-iron. I n austenite and in pure iron stable a t lOOO" the crystals possess a face-centred cubic lattice. This is also characteristic of y-iron and thereby a fundamental difference is established between a-iron and y-iron.In martensite the iron occurs in its a-modification. This is also the case with high speed tool steel which has been hardened a t 1275". Photo- micrographs of some of the preparations examined are included in E. P. POLUSHKIN (Iron and Steel Inst. Carnegie Xchol. Mem. 1920 10 129-150; cf. Rev. iietal. 1920,17 421).-Alloys of iron with uranium are pyrophoric this property varying directly with the content of uranium. Alloys containing carbon are decomposed by water but this effect is not J. F. S. Crystalline Structure of Iron and Steel. the paper. J. I?. x. Alloys of Iron and Uranium.INORGANIC CHEMISTRY. ii. 163 exhibited by silicon except when present in very large amount or by vanadium.A polished sample placed on the emulsion of a photographic plate leaves an impression which after development by the usual process represents the structure of the specimen. Iron-uranium alloys contain the uranium carbides UC U,C and U,C the compound Fe,C,U,C as well as the compounds V,C Pe6U and FeSi. Neither uranium nor any of its compounds already mentioned forms solid solutions with iron. Vanadium has a greater affinity for uranium than for carbon. Equilibria in the System Fe-C-8 the Equilibrium FeB-Martensite-~errQ~ Oxide-Gas. W. REINDERS and P. VAN GRONINGEN (Rec. trav. chirn. 1921 40 701-706).-A considerable number of determinations of points of univariant equilibrium for this system have been carried out. The conclusion is drawn that the transition temperature for Fes + Fe is 905"; this is in accord with previous results obtained by different methods. By extrapolation of the graphic results the quintuple point of the system is found a t 740" and 2300 mm.Researches on the Metallic Carbonyls. ROBERT LUDWIG MOND and ALBERT EDWARD WALLIS (T. 1922 121 29-32). The Action of Nitric Oxide on the Metallic Carboiiyls. ROBERT LUDWIG MOND and ALBERT EDWARD WALLIS (T. 1922 Expansion of Chromium and of Nickel-Chromium Alloys over a Wide Range of Temperatures. P. CHEVENARD ( C m p t . rend. 1992,174 109-112).-Between 0" and 100" the expansion of chromium is exactly reversible the curve showing no singular point. The true coefficient of expansion which is 6.8 x 10-6 a t O" increases rapidly with the temperature but the curve shows a slight concavity towards the increasing temperature.Nickel-chromium alloys containing up to 16% of chromium and from 0.5 to 2.5:/ of manganese were examined over the tempera- ture range 0" to 1000". The addition of chromium leads to a very rapid weakening of Che anomaly of dilatation of nickel and when the chromium content reaches 5yo the anomaly disappears. The addition of chromium to nickel affects the expansion of this metal very little a t the ordinary temperature but tends to increase i t a t higher temperatures ; this effect being probably due to the presence of the compound Ni,Cr3. J. W. MARDEN and M. N. RICH (Bur. Mines BUZZ. 1921 186 146 pp. ; cf. A. 1920 ii 547).-The work is divided into four parts dealing successively with an historical review of zir- conium minerals the salts of zirconium and the metal; experi- mental work on zirconium ; the furnaces used ; and a bibliography of zirconium and its compounds.Analytical methods are given for the estimation of zirconium in ferrozirconium steel alloys such as nickel-zirconium and a method of separation of titanium columbium tantalum and zirconium. The physical and chemical CHEMICAL ABSTRACTS. H. J. E. 121 32-33). W. G. Zirconium.ii. 154 ABSTRACTS O F CHEMICAL. PAPERS. properties of amorphous and coherent zirconium are described. The cupferron method is the only one effecting complete separation of zirconium from aluminium. Polymorphic Transformations of Anthony Trisulphide. SAMUEL WILSON and C. R. MCCROSKY ( J . Amer. Chem. SOC. 1921 43,2178-2179).-The rate of transformation of the red amorphous variety of antimony trisulphide into the black variety has been determined in the presence of N - 7N- 12N-hydrochloric acid 7N-phosphoric acid 7N-sulphuric acid glacial and N-acetic acids and a saturated ethereal solution of hydrochloric acid. Of these acid solutions only the aqueous solution of hydrochloric acid gave any appreciable transformation a t 18-22' even after two months. With the aqueous hydrochloric acid the time necessary for complete transformation was 0-5 day 1 day and 10.5 days for E N 7N and N respectively. The action is due to a solution of the red variety and a reprecipitation of the less soluble black variety. The effect of temperature was investigated with a 20% aqueous hydrochloric acid. Complete conversion a t 26.5" required forty- four hours ; a t 30" twenty-nine hours ; 35" sixteen hours ; 40' nine hours ; 68.5" sixty-two minutes and 75" thirty-two minutes. A 20% solution of hydrobromic acid gave no change after twenty hours a t 75". CHEMICAL ABSTRACTS. J. F. S.

ISSN:0368-1769    

DOI:10.1039/CA9222205140

出版商:RSC    

年代:1922

数据来源: RSC